CN103606671B - A kind of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof - Google Patents
A kind of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof Download PDFInfo
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- CN103606671B CN103606671B CN201310658516.0A CN201310658516A CN103606671B CN 103606671 B CN103606671 B CN 103606671B CN 201310658516 A CN201310658516 A CN 201310658516A CN 103606671 B CN103606671 B CN 103606671B
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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
- H01M4/52—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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Abstract
A kind of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof, this positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery molecular formula is Li
ani
1-x(MM ')
xo
2m ' ' O, wherein a=0.9-1.2,0≤x≤0.70, M is at least one in Co, Mn, Al; M ' is at least one in Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn, Ta; M ' ' O is coating layer, and M ' ' is Co and Al.The present invention also comprises the preparation method of described positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery.Materials processing performance of the present invention is outstanding, uses battery prepared by material of the present invention, cycle performance and high voltage capability excellence, and use safety is stablized, and both can meet the serviceability requirement of portable electric appts to battery, is suitable for again the type battery use that is used as power.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, especially relate to a kind of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof.
Background technology
Enter 21 century, the day by day exhaustion of the traditional energy such as coal, oil, efficient, environmental protection, reproducible secondary energy sources become the focus that people pay close attention to.As the representative of new forms of energy, lithium ion battery has been widely used in the fields such as electronic product, portable computer, electric tool, energy storage stand-by power supply, the vehicles, plays very important role, plays irreplaceable effect.
Along with making rapid progress of science and technology, the requirement of people to lithium ion battery is also more and more higher, and light, high-energy-density, safety non-toxic are the Main way of Future New Energy Source battery system development.Tradition positive pole material of lithium cobalt acid has stable electrical property, but price is higher, and its reality can utilize capacity to only have the half of its theoretical capacity (274mAh/g), about about 140mAh/g; Want to obtain higher capacity, then may affect cycle life and there is potential safety hazard.The spinel structure LiMn2O4 of low cost, although have the advantage of cost and security performance aspect, its high temperature circulation and irreversible manganese problems of dissolution when storing, and too low energy density (tap density <2.3g/cm
3, gram volume is about about 100mAh/g) and become the difficult problem restricting its extensive use.And be sent to the LiFePO4 of great expectations in recent years, then because the intrinsic defect of its material self, as not good in cryogenic property, poor processability, energy density are low, and the sight line of people of day by day fading out.
Nickel based material enjoys expectation because having higher energy density always, and on the one hand, its actual capacity is higher, can reach 190-210 mAh/g; On the other hand, it is far smaller than LiCoO to the pollution of environment
2, and price and resource aspect are all than LiCoO
2have more advantage.LiNiO
2have and LiCoO
2identical layer structure, wherein, oxygen atom is positioned at 6c position, for cubic closest packing, nickle atom is positioned at 3a position, and lithium atom is positioned at 3b position, alternately occupy octahedral site, in layered arrangement (cell parameter a=0.2886nm, c=1.4214nm) in 111 crystal plane direction.Oxygen atom is with the cubic structure close packed array of distortion a little, and lithium atom and nickle atom are alternately distributed in oxygen layer both sides, occupies its octahedral interstices.The NiO of crystal laminate
2for lithium ion provides the two-dimentional tunnel that can supply migration.Therefore, the stability of this layer structure determines LiNiO
2the quality of cycle performance.Owing to synthesizing LiNiO under usual high temperature
2during material, easily generate the Li of non-metering ratio
1-xni
1+xo
2, wherein have Ni
2+ion exists.Ni
2+ion is easy to occupy Li
+the position at place, and cause so-called " cation mixing " phenomenon to occur.In charge and discharge process, Ni
2+be oxidized to Ni
3+or Ni
4+, ([LiO between compound layer can be caused
6] octahedral layer) local collapse of structure, increase Li in discharge process
+the difficulty that ion embeds, causes the decline of discharge capacity, and cycle performance is deteriorated.In addition, LiNiO
2under height takes off lithium state, easily generate the very strong Ni of oxidizability
4+, not only oxidation Decomposition electrolyte, releases heat and gas, and self is unstable, easily decomposes and separates out O at a certain temperature
2, thus cause battery system to destroy the security incidents such as even blast.Thus, the inferior position of cycle performance and security performance aspect limits LiNiO greatly
2extensive use.
Large quantity research shows, to stratiform LiNiO
2carry out doping Co element modified, effectively can improve cycle performance and the security performance of material.Stratiform LiNi
1-xco
xo
2(0≤x≤1) is LiCoO
2and LiNiO
2solid solution, there is α-NaFeO
2type layer structure, belongs to cubic system, and space group is
, wherein lithium atom occupies octahedra 3a position, and cobalt atom and nickle atom occupy octahedra 3b position randomly, and oxygen atom occupies 6c position.LiNi
1-xco
xo
2cell parameter between LiCoO
2and LiNiO
2between, along with cobalt content minimizing (x), lattice parameters a and c increases.X value is to LiNi
1-xco
xo
2electrochemical Performances is comparatively large, can obtain outstanding cycle performance, and when x value reduces, the specific capacity of material is greatly increased when general x value is larger.But, although adding of Co makes LiNiO
2safety and cycle performance all be improved significantly, but to commercial applications be carried out, also need to solve LiNi further
1-xco
xo
2the problem such as the bigger than normal and cycle performance of irreversible capacity is not first good.
Based on this situation, Many researchers is at LiNiO
2the middle elements such as Co, Al and Mn that simultaneously adulterate, form LiNi
1-x-yco
xm
yo
2compound, to improve security performance and the cycle performance of material.Dsc analysis result shows, the LiNi formed after mixing Al
0.8co
0.15al
0.05o
2material with do not mix compared with Al product, rise to 310 DEG C with the thermal response temperature of oxygen by 200 DEG C, namely thermal stability and security performance are obviously promoted.
At present, although rich nickel material is by modified optimizations such as doping, performance has obtained very large lifting, but it will realize commercial applications, needs emphasis to promote processing characteristics, cycle performance and security performance.
Li
ani
1-xm
xo
2the lithiated compound of to be a kind of with Ni be matrix, there is layered crystal structure, capacity is high, advantage of lower cost, but material thermal stability is not good, surface basicity is higher, easy water suction, easy aerogenesis, poor processability, in charge and discharge process, crystal structure is unstable, and chemical property easily worsens and there is potential safety hazard.During charging, the Li in material
+deviate from, Ni in lattice
2+be oxidized to Ni
3+and Ni
4+ion, and the Ni ion of high-valence state easily with electrolyte generation side reaction and dissolving, can affect the electrical property of material on the one hand, another aspect easily produces gas, release heat, causes the problem of secure context; During electric discharge, Li
+embed lattice, the high price Ni ion reduction of material internal is Ni
2+, and Ni
2+with Li
+ionic radius more close, easily there is Ni
2+occupy original Li
+position and cause Li
+the situation that cannot embed, causes capacity attenuation and decrease in efficiency.
At present, the stratiform nickel-rich positive pole material (LiNi of synthesis
1-xm
xo
2) main defect is: 1, material surface basicity is high, and processing characteristics is bad, requires high to battery production environment, easily causes pole piece to fall the phenomenons such as material, battery water suction and bulging; 2, material and compatibility of electrolyte poor, easily there is side reaction, cause material property deterioration; 3, material structure less stable, high-temperature behavior is not good, overcharges, the security performance such as hot case is restricted; 4, the energy density of material under conventional voltage can't meet electrokinetic cell demand, need improve the charging voltage upper limit, booster tension platform and energy density.
Based on above defect, stratiform nickel-rich positive pole material is restricted in commercial applications, particularly cannot use on a large scale in motive-power battery.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and provide a kind of cycle performance better, use safety is stablized, and high voltage capability is positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof preferably.
Lithium salts, the additive M ' such as rich nickel multicomponent material presoma and, lithium carbonate mix with certain proportion by the present invention, and mixture generates rich nickel multicomponent material after high-temperature heat treatment, and it is coated this material to be carried out cobalt aluminium interaction surface deposition, obtains target product.
The positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery of the present invention, molecular formula is Li
ani
1-x(MM ')
xo
2m ' ' O, wherein a=0.9-1.2,0≤x≤0.70, M is at least one in Co, Mn, Al; M ' is at least one in Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn, Ta; M ' ' O is coating layer, and M ' ' is Co and Al, can also comprise Li or/and P;
Further, described coating layer is LiCoO
2, Co
3o
4, CoO, Co
2o
3, Al
2o
3, Li
3pO
4, AlPO
4, LiCoAlO
2, LiAlO
2in at least one, but Co and Al must be contained simultaneously.
The preparation method of the positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery of the present invention, comprises the following steps:
(1) Li/ (M+M '+Ni)=0.9-1.2 takes rich nickel multicomponent material presoma Ni in molar ratio
1-xm
x(OH)
2, lithium raw material, the oxide of additive M ' or hydroxide, then in mixing equipment, the preferred 60-65min of 15-300min(is mixed), then by mixture in air, oxygen or nitrogen atmosphere, through 500-1100 DEG C of high temperature sintering 5-20 hour (preferred 10-12 hour), generate rich nickel multicomponent material Li
ani
1-x(MM ')
xo
2;
Described lithium raw material is lithium carbonate or lithium hydroxide;
Described M ' is one or more in Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn, Ta;
Described mixing equipment preferably tiltedly mixes the one in machine, ball mill, efficient dry-mixed machine;
(2) aluminium compound is dissolved in deionized water or absolute ethyl alcohol, be mixed with the preferred 0.2-2mol/L of 0.1-10mol/L() solution, dripping precipitation reagent control ph is 3-10, and obtain aluminium covering liquid solution A, in described solution A, Al content is the 0.01%-0.5% of rich nickel multicomponent material weight;
Described aluminium compound is preferably the one in aluminum sulfate, aluminum nitrate, aluminium isopropoxide, aluminum phosphate;
Described precipitation reagent is preferably at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor;
(3) cobalt compound is dissolved in deionized water, is mixed with the preferred 0.2-2mol/L of 0.1-10mol/L() solution, dripping precipitation reagent control ph is 3-10, and obtain cobalt covering liquid solution B, in solution B, Co content is the 0.05%-5% of rich nickel multicomponent material weight;
Described cobalt compound is the one in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate;
Described precipitation reagent is at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor;
(4) rich for step (1) gained nickel multicomponent material is dropped in mixing equipment with the lithium compound of the 0%-1% being equivalent to rich nickel multicomponent material quality, add the solution A prepared by step (2) while stirring with the rotating speed of 100-2000rpm, the solution B prepared by step (3) (controls fluid injection speed, ensure that two kinds of solution add simultaneously), mix the preferred 30-60min of 5-100min(again), obtain the rich nickel multicomponent material that A, B solution are evenly coated; By this material in air, oxygen or nitrogen atmosphere, at temperature 200-1000 DEG C, sinter 2-12 hour, then cross 250-350 mesh sieve, to obtain final product;
Described lithium compound is the one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate;
Described mixing equipment is dispersion machine, high speed mixer, de-airing mixer etc.
The present invention mainly solves lithium ion battery stratiform nickel-rich positive pole material (Li
ani
1-xm
xo
2wherein a=0.9-1.2,0≤x≤0.70, M is one or more in Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn, Ta) aspect such as energy density, processing characteristics, cycle performance, security performance is in actual applications not enough.
The present invention adopts body phase compound substitute doping and the coated two kinds of modes of surface recombination deposition to carry out modification to rich nickel multicomponent material; By doping, the metallic element added and nickel ion form composite bed, nickel ion keeps electro-chemical activity, and Addition ofelements can replace part of nickel, ion size is stablized, and bonding force is strong, plays a supporting role in layered crystal structure, effectively can reduce the distortion distortion of lattice in charge and discharge process and in high temperature high voltage situation, make material structure more stable; By coated, netted interactive lithium aluminium cobalt compound coating layer is formed on stratiform nickel-rich positive pole material top layer, after heat treatment form uniform and stable, the exsertile shell of conductivity, shell can isolate electrolyte, reduce the side reaction between material body and electrolyte, reduce nickel stripping quantity, promote cycle performance and the security performance of material; On the other hand, the residual alkali in shell energy neutralization materials surface, reduces material basicity, thus reduces material to the susceptibility of moisture content in environment, promotes materials processing performance; This outer shell or excellent ion, electronic conductive layer, can accelerate interface conduction, promotes efficiency and the multiplying power of material.After being optimized by two kinds of means, the material circulation performance obtained is given prominence to, and security performance is outstanding, and processing characteristics is stablized, and can meet high temperature, high voltage, high power capacity electrokinetic cell system demand simultaneously.
The present invention compared with prior art, have the following advantages: composite mixed by adding special elements, suppress the distortion of lattice of material in charge and discharge process, improve the structural stability of material, the thermal stability of material, cycle performance, security performance are obviously promoted; By Surface coating process, form the homogeneous coating layer of one deck on rich nickel multicomponent material surface, make between material body and electrolyte, to form one deck passivating film, stop the side reaction between material and electrolyte, prevent Ni
4+ion and electrolyte react, release heat, output gas and the potential safety hazard that causes, effectively maintain material structure stability on the one hand, promote the security performance of material on the other hand.In addition, compound coating can prevent too much Li to be enriched in material surface, thus effective control LiOH concentration, reduce pH value, effectively prevent from making the water suction in battery pole piece process, foam, falling the phenomenons such as material, improve drawing abillity greatly, reduce material to the susceptibility of the indexs such as humidity in battery production environment simultaneously; Products obtained therefrom is spheric granules, and particle diameter D50 is 5-15 micron, and tap density is at 2.0-2.6 g/cm
3, pH≤11.8; Full battery 4.3V initial capacity can reach 160-200mAh/g, and 4.3,4.35V, 45 degree of circulations are after 500 weeks, capability retention>=80%; High-temperature behavior, over-charging all by.
Materials processing performance of the present invention is outstanding, uses battery prepared by material of the present invention, cycle performance and high voltage capability excellence, and use safety is stablized, and both can meet the serviceability requirement of portable electric appts to battery, is suitable for again the type battery use that is used as power.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum (XRD) (Cu harrows Ka ray, wavelength 0.154056nm) of the rich nickel multicomponent material in the embodiment of the present invention 1;
Fig. 2 is electronic scanning Electronic Speculum (SEM) photo of rich nickel multicomponent material in the embodiment of the present invention 1, and multiplication factor is 1000 times;
Fig. 3 is the cyclic curve of rich nickel multicomponent material in the embodiment of the present invention 2, and wherein: charge-discharge magnification is 0.5C, charging/discharging voltage is 3.0-4.3V.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
The preparation method of the positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take 3000g rich nickel multicomponent material presoma
0.6co
0.2mn
0.2(OH)
2), 1311g lithium carbonate, 10.5g zirconia, 31.2g magnesium oxide, to drop in ball grinder mixing 240 minutes, the raw material mixed put into Muffle furnace, in air atmosphere, 890 DEG C of sintering 12 hours, obtain rich nickel multicomponent material (molecular formula Li (Ni
0.6co
0.2mn
0.2)
0.977zr
0.003mg
0.02o
2);
(2) taking 10.2g aluminum nitrate is dissolved in deionized water, is mixed with the solution of 2.5mol/L, drips sodium hydroxide solution and regulates solution ph to 5.5, obtain aluminium covering liquid solution A;
(3) taking 20.8g cobalt nitrate is dissolved in deionized water, is mixed with the solution of 3mol/L, regulating solution ph to 6.0, obtaining cobalt covering liquid solution B by dripping sodium hydroxide solution;
(4) rich for 2000g step (1) gained nickel multicomponent material, 2.6g lithium hydroxide are dropped in dispersion machine, while stir limit implantation step (2) gained aluminium covering liquid and step (3) gained cobalt covering liquid simultaneously with the speed of 1000rpm, control fluid injection speed, ensure that two kinds of solution add simultaneously; Stir 50min after adding solution, coated good material is put into Muffle furnace, in air atmosphere, material, after 5 hours, is crossed 300 mesh sieves, to be obtained final product by 550 DEG C of heat treatments.
The present embodiment products obtained therefrom granularity D50=9.3um, pH=10.97, specific area BET=0.39m
2/ g, tap density=2.32g/cm
3.
Active material, PVDF and acetylene black are pressed the mass ratio mixing of 94:3:3, add NMP, stir and make slurry.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; Using metal lithium sheet as negative plate; Barrier film is the polypropylene microporous barrier (Celgard 2400) of import; Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into CR2032 experimental button cell in glove box.The charge-discharge performance test of battery is at room temperature carried out, and adopt the mode of first constant current constant voltage again to charge, charge cutoff voltage is 4.4V, adopt constant-current discharge, cut-ff voltage is 3.0V, and the density of charging current is 0.2C multiplying power, and first charge-discharge efficiency and specific discharge capacity are 91.7% and 192.7mAh/g.
Accompanying drawing 1 is the X ray diffracting spectrum (XRD) of product, and accompanying drawing 2 is electronic scanning Electronic Speculum (SEM) photo of product.
Embodiment 2
The preparation method of the positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take 3000g rich nickel multicomponent material presoma
0.7co
0.2al
0.1(OH)
2), 1273g lithium hydroxide, 20.1g titanium dioxide (TiO
2), 10.8g zirconia (ZrO
2), 33.8g magnesium oxide to drop in ball grinder mixing 200 minutes, and the raw material mixed is put into clock hood type furnace, under oxygen atmosphere, 875 DEG C of sintering 14 hours, obtain rich nickel multicomponent material;
(2) taking 12.1g aluminum phosphate is dissolved in deionized water, is mixed with the solution of 2mol/L, by dripping NaOH and ammonia spirit adjustment solution ph to 8, obtains aluminium covering liquid solution A;
(3) taking 100.5g cobaltous sulfate is dissolved in deionized water, is mixed with the solution of 5mol/L, regulating solution ph to 8, obtaining cobalt covering liquid solution B by dripping sodium hydroxide solution;
(4) rich for 2500g step (1) gained nickel multicomponent material is dropped in dispersion machine, while stir limit implantation step (2) gained aluminium covering liquid and step (3) gained cobalt covering liquid simultaneously with the speed of 1000rpm, control fluid injection speed, ensure that two kinds of solution add simultaneously; Stir 60min after adding solution, coated good material is put into Muffle furnace, material, after 8 hours, is crossed 300 mesh sieves, to be obtained final product by 750 DEG C of heat treatments.
The present embodiment products obtained therefrom granularity D50=11.8um, pH=11.15, specific area BET=0.45m2/g, tap density=2.47g/cm3; Product is assembled into CR2032 type button cell by embodiment 1 mode and carries out electrochemical property test, accompanying drawing 3 is circulating battery curve, and wherein contrasting sample is material (namely without the present invention's doping and the material of coated process) without modification of the present invention.
Embodiment 3
The preparation method of the positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take 3000g rich nickel multicomponent material presoma
0.75co
0.1mn
0.1al
0.05(OH)
2), 1301g lithium hydroxide, 22.9g aluminium oxide, 50.3g yittrium oxide to drop in ball grinder mixing 200 minutes, and the raw material mixed is put into clock hood type furnace, under oxygen atmosphere, 915 DEG C of sintering 10 hours, obtain rich nickel multicomponent material;
(2) taking 12.1g aluminum nitrate is dissolved in deionized water, is mixed with the solution of 2mol/L, drips sodium hydroxide solution and regulates solution ph to 8.5, obtain aluminium covering liquid solution A;
(3) taking 100.5g cobalt acetate is dissolved in deionized water, is mixed with the solution of 5mol/L, regulating solution ph to 8.5, obtaining cobalt covering liquid solution B by dripping sodium hydroxide solution;
(4) rich for 2500g nickel multicomponent material is dropped in dispersion machine, while stir limit with the speed of 1000rpm to inject aluminium covering liquid and cobalt covering liquid simultaneously, control fluid injection speed, ensure that two kinds of solution add simultaneously; Stir 60min after adding solution, coated good material is put into Muffle furnace, material, after 8 hours, is crossed 300 mesh sieves, is namely obtained target product by 780 DEG C of heat treatments.
The present embodiment products obtained therefrom granularity D50=12.5um, pH=11.21, specific area BET=0.36m2/g, tap density=2.36g/cm3; Assembling product is become 063048 type rectangular cell, table 1 is that active material, PVDF and the conductive black mass ratio by 95.5:2.3:2.2 (mixes, adds NMP, stir and make slurry by battery testing data.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; 063048 type battery is assembled into negative plate, barrier film, electrolyte etc.The charge-discharge performance test of battery is at room temperature carried out, and adopt the mode of first constant current constant voltage again to charge, charge cutoff voltage is 4.35V, and adopt constant-current discharge, cut-ff voltage is 3.0V, and the density of charging current is 0.5C multiplying power.Not through overdoping and coated material before modified).
Claims (9)
1. a positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery, is characterized in that, molecular formula is Li
ani
1-x(MM ')
xo
2m ' ' O, wherein a=0.9-1.2,0<x≤0.70, M is at least one in Co, Mn, Al; M ' is at least one in Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn, Ta; M ' ' O is coating layer, and M ' ' comprises Co and Al;
Its preparation method, comprises the following steps:
(1) Li/ (M+M '+Ni)=0.9-1.2 takes rich nickel multicomponent material presoma Ni in molar ratio
1-xm
x(OH)
2, lithium raw material, the oxide of additive M ' or hydroxide, then in mixing equipment, mix 15-300min, then by mixture in air or oxygen atmosphere, through 500-1100 DEG C of high temperature sintering 5-20 hour, generate rich nickel multicomponent material Li
ani
1-x(MM ')
xo
2;
(2) be dissolved in deionized water or absolute ethyl alcohol by aluminium compound, be mixed with the solution of 0.1-10mol/L, dripping precipitation reagent control ph is 3-10, and obtain aluminium covering liquid solution A, in described solution A, Al content is the 0.01%-0.5% of rich nickel multicomponent material weight;
(3) be dissolved in deionized water by cobalt compound, be mixed with the solution of 0.1-10mol/L, dripping precipitation reagent control ph is 3-10, and obtain cobalt covering liquid solution B, in solution B, Co content is the 0.05%-5% of rich nickel multicomponent material weight;
(4) rich for step (1) gained nickel multicomponent material is dropped in mixing equipment with the lithium compound of the 0%-1% being equivalent to rich nickel multicomponent material quality, the solution A prepared by step (2), the solution B prepared by step (3) is added while stirring with the rotating speed of 100-2000rpm, control fluid injection speed, two kinds of solution are added simultaneously, continue to be uniformly mixed 5-100min, obtain the rich nickel multicomponent material that A, B solution are evenly coated; By this material in air or oxygen atmosphere, at temperature 200-1000 DEG C, sinter 2-12 hour, then cross 250-350 mesh sieve, to obtain final product.
2. positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1, is characterized in that, M ' ' also comprises Li or/and P.
3. positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1, is characterized in that, described coating layer is LiCoO
2, Co
3o
4, CoO, Co
2o
3, Al
2o
3, Li
3pO
4, AlPO
4, LiCoAlO
2, LiAlO
2in at least one.
4. positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, is characterized in that, in its preparation methods steps (1), described lithium raw material is lithium carbonate or lithium hydroxide.
5. the preparation method of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, is characterized in that, in its preparation methods steps (2), described aluminium compound is the one in aluminum sulfate, aluminum nitrate, aluminium isopropoxide, aluminum phosphate.
6. the preparation method of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, it is characterized in that, in its preparation methods steps (2), described precipitation reagent is at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor.
7. the preparation method of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, is characterized in that, in its preparation methods steps (3), described cobalt compound is the one in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate.
8. the preparation method of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, it is characterized in that, in its preparation methods steps (3), described precipitation reagent is at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor.
9. the preparation method of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery according to claim 1 and 2, is characterized in that, in its preparation methods steps (4), described lithium compound is the one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate.
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Families Citing this family (25)
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| CN104393281B (en) * | 2014-12-03 | 2017-01-25 | 梁贺君 | Preparation method of manganese, nickel and lithium cathode material |
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| CN117254020B (en) * | 2023-11-13 | 2024-03-08 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556551A (en) * | 2003-12-30 | 2004-12-22 | 中国科学院上海微系统与信息技术研究 | Surface covering material of lithium ion battery positive electrode and its technology |
| CN101212048A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Anode material of Li-ion secondary battery and battery containing the same |
| CN101997113A (en) * | 2009-08-17 | 2011-03-30 | 北京当升材料科技股份有限公司 | Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof |
| CN102347471A (en) * | 2010-08-02 | 2012-02-08 | 清华大学 | Lithium-nickel-cobalt-manganese oxide composite material particle and preparation method thereof as well as battery |
| CN102354750A (en) * | 2011-10-11 | 2012-02-15 | 北京化工大学 | LiCo0.75Al0.25O2-cladded LiNiO2 electrode material and preparation method thereof |
| CN102496710A (en) * | 2011-12-31 | 2012-06-13 | 湖南杉杉户田新材料有限公司 | Nickel-based multiple components cathode material and its preparation method |
| CN102856530A (en) * | 2011-06-30 | 2013-01-02 | 清华大学 | Lithium ion battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4161382B2 (en) * | 1997-02-25 | 2008-10-08 | 堺化学工業株式会社 | Process for producing two-layer structured particulate composition |
| US9054374B2 (en) * | 2005-05-17 | 2015-06-09 | Sony Corporation | Cathode active material, method of manufacturing the same and battery |
| JP5556983B2 (en) * | 2007-12-28 | 2014-07-23 | 戸田工業株式会社 | Lithium manganate for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
-
2013
- 2013-12-09 CN CN201310658516.0A patent/CN103606671B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556551A (en) * | 2003-12-30 | 2004-12-22 | 中国科学院上海微系统与信息技术研究 | Surface covering material of lithium ion battery positive electrode and its technology |
| CN101212048A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Anode material of Li-ion secondary battery and battery containing the same |
| CN101997113A (en) * | 2009-08-17 | 2011-03-30 | 北京当升材料科技股份有限公司 | Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof |
| CN102347471A (en) * | 2010-08-02 | 2012-02-08 | 清华大学 | Lithium-nickel-cobalt-manganese oxide composite material particle and preparation method thereof as well as battery |
| CN102856530A (en) * | 2011-06-30 | 2013-01-02 | 清华大学 | Lithium ion battery |
| CN102354750A (en) * | 2011-10-11 | 2012-02-15 | 北京化工大学 | LiCo0.75Al0.25O2-cladded LiNiO2 electrode material and preparation method thereof |
| CN102496710A (en) * | 2011-12-31 | 2012-06-13 | 湖南杉杉户田新材料有限公司 | Nickel-based multiple components cathode material and its preparation method |
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