CN103606671A - Positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof - Google Patents
Positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof Download PDFInfo
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- CN103606671A CN103606671A CN201310658516.0A CN201310658516A CN103606671A CN 103606671 A CN103606671 A CN 103606671A CN 201310658516 A CN201310658516 A CN 201310658516A CN 103606671 A CN103606671 A CN 103606671A
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a positive electrode material of a high-capacity dynamic-type nickel-rich lithium ion battery and a preparation method. The molecular formula of the positive electrode material of the high-capacity dynamic-type nickel-rich lithium ion battery is LiaNi1-x(MM')xO2.M''O, wherein a is equal to 0.9-1.2, x is more than or equal to 0 and less than or equal to 0.7, and M is at least one of Co, Mn and Al; M' is at least one of Co, Al, V, Mn, Zr, Mg, Ti, Cr, Zr, La, Ce, Pr, Nd, Nb, Mo, Y, Sr, Ba, B, Sr, Sn and Ta; M''O is a cladding layer, and M'' is Co and Al. The invention also relates to a preparation method for the positive electrode material of the high-capacity dynamic-type nickel-rich lithium ion battery. The material machining performance is excellent, the battery prepared by utilizing the material, the cycling performance and the high-voltage performance are excellent, the safety and stability in use can be realized, not only can the application performance requirement of a portable electronic device on the battery be met, but also the positive electrode material is applicable to the power battery.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, especially relate to rich nickel anode material for lithium-ion batteries of a kind of high power capacity power type and preparation method thereof.
Background technology
Enter 21 century, the day by day exhaustion of the traditional energies 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, is playing the part of very important role, is bringing into play irreplaceable effect.
Along with making rapid progress of science and technology, people are also more and more higher to the requirement of lithium ion battery, and light, high-energy-density, safety non-toxic are the main directions 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 half of its theoretical capacity (274mAh/g), about 140mAh/g left and right; Want to obtain higher capacity, may affect cycle life and have potential safety hazard.Spinel structure LiMn2O4 cheaply, although have the advantage of cost and security performance aspect, irreversible manganese dissolution problems when its high temperature circulation and storage, and too low energy density (tap density <2.3g/cm
3, the about 100mAh/g of gram volume left and right) and become the difficult problem of its extensive use of restriction.And be sent in recent years the LiFePO4 of great expectations, and because the intrinsic defect of its material self, as cryogenic property is not good, poor processability, energy density be low etc., and the people's of day by day fading out sight line.
Nickel based material enjoys expectation because having compared with high energy density always, and on the one hand, its actual capacity is higher, can reach 190-210 mAh/g; On the other hand, its pollution to environment is far smaller than LiCoO
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 111 crystal plane direction, be layered arrangement (cell parameter a=0.2886nm, c=1.4214nm).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, occupy its octahedral interstices.The NiO of crystal laminate
2for providing, lithium ion can supply the two-dimentional tunnel of migration.Therefore, the stability of this layer structure has determined LiNiO
2the quality of cycle performance.Owing to conventionally synthesizing LiNiO under 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+, can cause ([LiO between compound layer
6] octahedral layer) local collapse of structure, increase Li in discharge process
+the difficulty that ion embeds, causes the decline of discharge capacity, cycle performance variation.In addition LiNiO,
2under the de-lithium state of height, easily generate the Ni that oxidizability is very strong
4+, not only oxidation Decomposition electrolyte, emits heat and gas, and self is unstable, easily decomposes at a certain temperature and separates out O
2thereby, cause battery system to destroy the security incidents such as even blast.Thereby the inferior position of cycle performance and security performance aspect is limiting LiNiO greatly
2extensive use.
Large quantity research shows, to stratiform LiNiO
2the Co that adulterates is element modified, can effectively 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 larger, and general x value can obtain outstanding cycle performance when larger, and when x value reduces, the specific capacity of material is greatly increased.Yet, although adding of Co makes LiNiO
2safety and cycle performance all be improved significantly, but to carry out commercial applications, also need further to solve LiNi
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, mixes the LiNi forming after Al
0.8co
0.15al
0.05o
2material is compared with not mixing Al product, rises to 310 ℃ with the thermal response temperature of oxygen by 200 ℃, and namely thermal stability and security performance are obviously promoted.
At present, although rich nickel material waits modified optimization by doping, performance has obtained very large lifting, yet it will realize commercial applications, needs emphasis to promote processing characteristics, cycle performance and security performance.
Li
ani
1-xm
xo
2it is the lithiated compound that a kind of Ni of take is matrix, there is layered crystal structure, capacity is high, and cost is relatively low, but material thermal stability is not good, surface basicity is higher, easily water suction, easy aerogenesis, poor processability, in charge and discharge process, crystal structure is unstable, and chemical property easily worsens and has a 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 dissolves with electrolyte generation side reaction, one side can affect the electrical property of material, easily produces on the other hand gas, and release heat causes the problem of secure context; During electric discharge, Li
+embed lattice, the high price Ni ion of material internal is reduced to Ni
2+, and Ni
2+with Li
+ionic radius more approaching, 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, synthetic stratiform nickel-rich positive pole material (LiNi
1-xm
xo
2) main defect is: 1, material surface basicity is high, and processing characteristics is bad, battery production environment is required high, easily causes that pole piece falls the phenomenons such as material, battery water suction and bulging; 2, material and compatibility of electrolyte are poor, and side reaction easily occurs, and cause material property deteriorated; 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, needs to 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 in motive-power battery, cannot use on a large scale.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides a kind of cycle performance better, uses safety and stability, and high voltage capability is rich nickel anode material for lithium-ion batteries of high power capacity power type and preparation method thereof preferably.
The present invention mixes lithium salts, the additive M ' such as rich nickel multicomponent material presoma and, lithium carbonate with certain proportion, mixture generates rich nickel multicomponent material after high-temperature heat treatment, this material is carried out to cobalt aluminium interaction surface deposition coated, obtains target product.
The present invention's the rich nickel anode material for lithium-ion batteries of high power capacity power type, molecular formula is Li
ani
1-x(MM ')
xo
2m ' ' O, a=0.9-1.2 wherein, 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 must contain Co and Al simultaneously.
The preparation method of the present invention's the rich nickel anode material for lithium-ion batteries of high power capacity power type, 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, additive M ' oxide or hydroxide, then in mixing equipment, mix the preferred 60-65min of 15-300min(), then by mixture in air, oxygen or nitrogen atmosphere, through 500-1100 ℃ of high temperature sintering 5-20 hour (preferably 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 is a kind of in mixed machine, ball mill, efficient dry-mixed machine preferably tiltedly;
(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 value is 3-10, obtains aluminium covering liquid solution A, and in described solution A, Al content is the 0.01%-0.5% of rich nickel multicomponent material weight;
Described aluminium compound is preferably a kind of 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, to control pH value be 3-10, obtains 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 a kind of 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) the rich nickel multicomponent material of step (1) gained and the lithium compound that is equivalent to the 0%-1% of rich nickel multicomponent material quality are dropped in mixing equipment, rotating speed with 100-2000rpm adds the prepared solution A of step (2), the prepared solution B of step (3) (to control fluid injection speed while stirring, guarantee that two kinds of solution add simultaneously), mix again the preferred 30-60min of 5-100min(), obtain A, the even coated rich nickel multicomponent material of B solution; By this material, in air, oxygen or nitrogen atmosphere, sintering 2-12 hour at temperature 200-1000 ℃, then crosses 250-350 mesh sieve, obtains;
Described lithium compound is a kind of 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 stratiform nickel-rich positive pole material (Li for lithium ion battery
ani
1-xm
xo
2a=0.9-1.2 wherein, 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 in actual applications, processing characteristics, cycle performance, security performance is not enough.
The present invention adopts the mutually compound substitute doping of body 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 adding and nickel ion form composite bed, nickel ion keeps electro-chemical activity, and add element, can replace part of nickel, ion dimensionally stable, bonding force is strong, in layered crystal structure, plays a supporting role, the distortion distortion that can effectively reduce lattice in charge and discharge process and in high temperature high voltage situation, makes material structure more stable; By coated, on stratiform nickel-rich positive pole material top layer, form netted interactive lithium aluminium cobalt compound coating layer, after heat treatment form uniform and stable, the exsertile shell of conductivity, shell can be isolated 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, thereby reduces the susceptibility of material to moisture content in environment, promotes materials processing performance; This outer shell or good ion, electronic conductive layer, can accelerate interface conduction, promotes efficiency and the multiplying power of material.After optimizing by two kinds of means, the material cycle performance obtaining is outstanding, and security performance is outstanding, and processing characteristics is stable, 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: by adding special elements composite mixed, suppress the distortion of lattice of material in charge and discharge process, improved the structural stability of material, the thermal stability of material, cycle performance, security performance are obviously promoted; By surface, be coated processing, on rich nickel multicomponent material surface, form the coating layer of one deck homogeneous, make to form one deck passivating film between material body and electrolyte, stop the side reaction between material and electrolyte, prevent Ni
4+ion reacts with electrolyte, release heat, output gas and the potential safety hazard that causes effectively maintains material structure stability on the one hand, promotes on the other hand the security performance of material.In addition, compound coating can prevent that too much Li is enriched in material surface, thereby effectively control LiOH concentration, reduce pH value, effectively prevent water suction in making battery pole piece process, foam, fall the phenomenons such as material, promote greatly drawing abillity, reduced the susceptibility of material to 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 circulations be after 500 weeks, capability retention>=80%; High-temperature behavior, over-charging all can pass through.
Materials processing performance of the present invention is outstanding, the battery that uses material of the present invention to prepare, and cycle performance and high voltage capability are excellent, use safety and stability, both can meet the serviceability requirement of portable electric appts to battery, and the type battery that is suitable for being again used as power is used.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum (XRD) (Cu rake 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 rich nickel anode material for lithium-ion batteries of high power capacity power type of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take the rich nickel multicomponent material of 3000g presoma
0.6co
0.2mn
0.2(OH)
2), 1311g lithium carbonate, 10.5g zirconia, 31.2g magnesium oxide, drop in ball grinder and mix 240 minutes, the raw material mixing is put into Muffle furnace, under air atmosphere, 890 ℃ 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) take 10.2g aluminum nitrate and be dissolved in deionized water, be mixed with the solution of 2.5mol/L, drip sodium hydroxide solution regulator solution pH value to 5.5, obtain aluminium covering liquid solution A;
(3) take 20.8g cobalt nitrate and be dissolved in deionized water, be mixed with the solution of 3mol/L, by dripping sodium hydroxide solution regulator solution pH value to 6.0, obtain cobalt covering liquid solution B;
(4) the rich nickel multicomponent material of 2000g step (1) gained, 2.6g lithium hydroxide are dropped in dispersion machine, limit implantation step (2) gained aluminium covering liquid and step (3) gained cobalt covering liquid are simultaneously stirred with the speed of 1000rpm in limit, control fluid injection speed, guarantee that two kinds of solution add simultaneously; After adding solution, stir 50min, the material being coated is put into Muffle furnace, in air atmosphere, 550 ℃ of heat treatments, after 5 hours, are crossed 300 mesh sieves by material, obtain.
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.
The mass ratio of active material, PVDF and acetylene black being pressed to 94:3:3 mixes, and adds NMP, stirs and makes slurry.Slurry is coated on aluminium foil, at 120 ℃, dried, 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, adopt first constant current again the mode of constant voltage 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.
The X ray diffracting spectrum (XRD) that accompanying drawing 1 is product, electronic scanning Electronic Speculum (SEM) photo that accompanying drawing 2 is product.
Embodiment 2
The preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take the rich nickel multicomponent material of 3000g 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 drops in ball grinder and mixes 200 minutes, and the raw material mixing is put into clock hood type furnace, under oxygen atmosphere, 875 ℃ of sintering 14 hours, obtain rich nickel multicomponent material;
(2) take 12.1g aluminum phosphate and be dissolved in deionized water, be mixed with the solution of 2mol/L, by dripping NaOH and ammonia spirit regulator solution pH value to 8, obtain aluminium covering liquid solution A;
(3) take 100.5g cobaltous sulfate and be dissolved in deionized water, be mixed with the solution of 5mol/L, by dripping sodium hydroxide solution regulator solution pH value to 8, obtain cobalt covering liquid solution B;
(4) the rich nickel multicomponent material of 2500g step (1) gained is dropped in dispersion machine, limit implantation step (2) gained aluminium covering liquid and step (3) gained cobalt covering liquid are simultaneously stirred with the speed of 1000rpm in limit, control fluid injection speed, guarantee that two kinds of solution add simultaneously; After adding solution, stir 60min, the material being coated is put into Muffle furnace, 750 ℃ of heat treatments, after 8 hours, are crossed 300 mesh sieves by material, obtain.
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, wherein contrasts sample for not passing through the material (without the present invention's doping and the coated material of processing) of modification of the present invention.
Embodiment 3
The preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type of the present embodiment, comprises the following steps:
(1) (molecular formula is Ni to take the rich nickel multicomponent material of 3000g presoma
0.75co
0.1mn
0.1al
0.05(OH)
2), 1301g lithium hydroxide, 22.9g aluminium oxide, 50.3g yittrium oxide drop in ball grinder and mix 200 minutes, and the raw material mixing is put into clock hood type furnace, under oxygen atmosphere, 915 ℃ of sintering 10 hours, obtain rich nickel multicomponent material;
(2) take 12.1g aluminum nitrate and be dissolved in deionized water, be mixed with the solution of 2mol/L, drip sodium hydroxide solution regulator solution pH value to 8.5, obtain aluminium covering liquid solution A;
(3) take 100.5g cobalt acetate and be dissolved in deionized water, be mixed with the solution of 5mol/L, by dripping sodium hydroxide solution regulator solution pH value to 8.5, obtain cobalt covering liquid solution B;
(4) the rich nickel multicomponent material of 2500g is dropped in dispersion machine, aluminium covering liquid and cobalt covering liquid are injected with the speed stirring limit of 1000rpm in limit simultaneously, control fluid injection speed, guarantee that two kinds of solution add simultaneously; After adding solution, stir 60min, the material being coated is put into Muffle furnace, 780 ℃ of heat treatments, after 8 hours, are crossed 300 mesh sieves by material, obtain target product.
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 to 063048 type rectangular cell, and table 1 is that battery testing data (are mixed active material, PVDF and conductive black, added NMP, stir and make slurry by the mass ratio of 95.5:2.3:2.2.Slurry is coated on aluminium foil, at 120 ℃, dried, make positive plate; Be assembled into 063048 type battery with negative plate, barrier film, electrolyte etc.The charge-discharge performance test of battery is at room temperature carried out, adopt first constant current again the mode of constant voltage charge, charge cutoff voltage is 4.35V, adopts constant-current discharge, cut-ff voltage is 3.0V, the density of charging current is 0.5C multiplying power.Before modification, be not through overdoping and coated material).
Claims (10)
1. the rich nickel anode material for lithium-ion batteries of high power capacity power type, is characterized in that, molecular formula is Li
ani
1-x(MM ')
xo
2m ' ' O, a=0.9-1.2 wherein, 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.
2. the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 1, is characterized in that, M ' ' is that Co, Al and Li are or/and P.
3. the rich nickel anode material for lithium-ion batteries of high power capacity power type 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. a method of preparing the rich nickel anode material for lithium-ion batteries of high power capacity power type as described in one of claim 1-3, is characterized in that, 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, additive M ' oxide or hydroxide, then in mixing equipment, mix 15-300min, then by mixture in air, oxygen or nitrogen atmosphere, through 500-1100 ℃ of high temperature sintering 5-20 hour, generate rich nickel multicomponent material Li
ani
1-x(MM ')
xo
2;
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;
(2) aluminium compound is dissolved in deionized water or absolute ethyl alcohol, is mixed with the solution of 0.1-10mol/L, dripping precipitation reagent control pH value is 3-10, obtains aluminium covering liquid solution A, and in described solution A, Al content is the 0.01%-0.5% of rich nickel multicomponent material weight;
(3) cobalt compound is dissolved in deionized water, is mixed with the solution of 0.1-10mol/L, dripping precipitation reagent control pH value is 3-10, obtains cobalt covering liquid solution B, and in solution B, Co content is the 0.05%-5% of rich nickel multicomponent material weight;
(4) the rich nickel multicomponent material of step (1) gained and the lithium compound that is equivalent to the 0%-1% of rich nickel multicomponent material quality are dropped in mixing equipment, rotating speed with 100-2000rpm adds the prepared solution A of step (2), the prepared solution B of step (3) while stirring, control fluid injection speed, two kinds of solution are added simultaneously, continue to be uniformly mixed 5-100min, obtain A, the even coated rich nickel multicomponent material of B solution; By this material, in air, oxygen or nitrogen atmosphere, sintering 2-12 hour at temperature 200-1000 ℃, then crosses 250-350 mesh sieve, obtains.
5. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, is characterized in that, in step (1), described lithium raw material is lithium carbonate or lithium hydroxide.
6. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, is characterized in that, in step (2), described aluminium compound is a kind of in aluminum sulfate, aluminum nitrate, aluminium isopropoxide, aluminum phosphate.
7. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, it is characterized in that, in step (2), described precipitation reagent is at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor.
8. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, is characterized in that, in step (3), described cobalt compound is a kind of in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate.
9. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, it is characterized in that, in step (3), described precipitation reagent is at least one in carbonic hydroammonium, phosphoric acid hydrogen ammonia, ammonium dihydrogen phosphate, NaOH, ammoniacal liquor.
10. the preparation method of the rich nickel anode material for lithium-ion batteries of high power capacity power type according to claim 4, is characterized in that, in step (4), described lithium compound is a kind of in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate.
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