CN1838453A - Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof - Google Patents

Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof Download PDF

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CN1838453A
CN1838453A CNA2005100313543A CN200510031354A CN1838453A CN 1838453 A CN1838453 A CN 1838453A CN A2005100313543 A CNA2005100313543 A CN A2005100313543A CN 200510031354 A CN200510031354 A CN 200510031354A CN 1838453 A CN1838453 A CN 1838453A
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nickel
cobalt
manganese
lithium
precipitation
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CN100362681C (en
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郭华军
李新海
王志兴
彭文杰
张明
胡启阳
张云河
杨志
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Central South University
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    • Y02E60/10Energy storage using batteries

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Abstract

This invention relates to lithium battery positive material of lithium, nickel, cobalt, manganese, oxygen, and their making method, the chemistry molecule formula as follows: Li1+deltaNixCoyMnzO2, wherein 1.02<1+delta<2,0.5<x+y+z<1. The preparation method includes the preparation of nickel cobalt manganese oxide, their blended solution's deposition and heat treatment. The raw material cost is only 1/3 of LiCoO2; and the method can improve the batter's volume energy density; the technology operation is easy to control. Comparing to the traditional LiCoO2 material, this invention can discharge around 2.75-4.6V, which has higher specific volume.

Description

A kind of lithium ion battery anode material lithium nickel cobalt manganese oxygen and preparation method thereof
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, particularly the lithium nickel cobalt manganese oxygen material.Belong to energy storage material and electrochemical field.
Background technology
Energy crisis and environmental pollution be human survival face sternly complete challenge, seeking clean, reproducible secondary energy sources is the tasks of realizing that human social needs to be resolved hurrily.In numerous secondary cell systems, lithium ion battery have operating voltage height, energy density big, have extended cycle life, advantages such as self-discharge rate is little, environmental protection, become the secondary cell main development tendency.Present commercial lithium ion battery negative material generally adopts graphite or graphitized carbon material, and its theoretical specific capacity is 372mAh/g, and actual capacity also reaches more than the 330mAh/g, and aboundresources, cheap.And positive electrode mainly adopts and has α-NaFeO 2The LiCoO of type layer structure 2, it has synthetic easy, the stable advantage of charge-discharge performance, but also comes with some shortcomings: because LiCoO 2In have only half lithium can be reversible deviate from/embed, its theoretical specific capacity is 147mAh/g, and actual use capacity is about 140mAh/g, 1/2nd of still not enough charcoal capacity of negative plates; LiCoO 2syntheticly need rare, the expensive cobalt metal of ample resources, thereby the cost of raw material of battery is higher; Charging state LiCoO 2Poor heat stability, make with LiCoO 2Not good enough for the lithium ion battery of positive pole in the fail safe under the abuse conditions, can not satisfy the needs of motive-power batteries such as electric vehicle power sources, thereby hinder the development of lithium ion battery.
In the substitution material of cobalt acid lithium, mainly contain olivine-type LiFePO 4, stratiform LiMnO 2, spinel-type LiMn 2O 4And stratiform LiNiO 2Deng.LiFePO wherein 4Have very excellent thermal stability, theoretical capacity is 170mAh/g, but actual capacity is below 140mAh/g, low (the about 3.4V vs Li of operating voltage +/ Li), electron conduction is poor, and the diffusion rate of lithium in solid phase is little, and high rate during charging-discharging is poor, thereby has limited the energy density and the power density of battery; Manganese-base oxide is because the prices of raw and semifnished materials that adopt are cheap, but all pure stratiform LiMnO 2Or the slight stratiform LiMnO that mixes 2In cyclic process, all there is transformation, and causes significant capacity attenuation to spinel structure; Spinel-type LiMn 2O 4Have the working voltage platform of 3.9-4.1V, and have fail safe preferably, but the specific capacity of this material is lower, the actual capacity that uses is 100-120mAh/g, and the high temperature charge-discharge performance is poor, structural instability; LiNiO 2Has the LiCoO of ratio 2Lower cost of material and higher specific capacity, but LiNiO 2Synthetic difficulty, be difficult to obtain the stoichiometric proportion product, and Ni 4+Very unstable under high voltage, so the cycle performance of material and thermal stability are very poor, all are difficult to satisfy the requirement of commercialization lithium ion battery and improve the specific capacity of positive electrode and the requirement that reduces cost.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anode material for lithium-ion batteries, make the atom content of prepared cell positive material cobalt in nickel cobalt manganese be lower than 15%; Reversible capacity>the 150mAh/g of this positive electrode between 2.75-4.3V, the reversible capacity>190mAh/g between the 2.75-4.6V, and have good cyclical stability and other chemical property.
A kind of lithium ion battery anode material lithium nickel cobalt manganese oxygen--rich lithium type layer structure lithium ion battery positive electrode, its chemical molecular formula is: Li 1+ δNi xCo yMn zO 2, 1.02<1+ δ<2,0.1<x<0.8,0.02<y<O.15 wherein, 0.1<z<0.8, and 0.5<x+y+z<1.
A kind of lithium ion battery anode material lithium nickel cobalt manganese oxygen preparation method comprises preparation, nickel, cobalt, the co-precipitation of manganese mixing salt solution, the heat treatment of cobalt-nickel-manganese oxide compound.Adopt the soluble-salt of nickel, cobalt, manganese to make raw material according to n Ni: n Co: n Mn=x: y: z is mixed with nickel, cobalt, the manganese mixing salt solution that concentration is 1-2mol/L, carries out co-precipitation then, and the soluble-salt of nickel, cobalt, manganese comprises sulfate or chloride or acetate;
Co-precipitation is a complexing agent with ammoniacal liquor or ammonium salt, LiOH or KOH or NaOH solution are precipitation reagent, join in the reactor with nickel salt solution, and ammonia concentration is 1g/L-17g/L in the control reaction system, temperature is that 25 ℃-80 ℃, pH value are 9-12, obtains the hydroxide of even codeposition nickel cobalt manganese.
Co-precipitation can also be made precipitation reagent with oxalic acid or oxalates or carbon dioxide or carbonate or bicarbonate, and the precipitation reagent of excessive 1%-10% and nickel, cobalt, the reaction of manganese mixing salt solution obtain the oxalates or the even codeposit of carbonate of nickel cobalt manganese.
Coprecipitated product is heat-treated at 400 ℃~700 ℃ after drying, obtains the composite oxides of nickel cobalt manganese;
With dried cobalt-nickel-manganese oxide compound is raw material, presses atomic ratio n with Li source compound Li: (n Ni+ n Co+ n Mn)=(1+ δ): mixed (x+y+z) is even, ball milling, and after 600 ℃~1000 ℃ high-temperature process, fragmentation, classification promptly gets rich lithium type Li 1+ δNi xCo yMn zO 2Positive electrode.Li source compound is lithium carbonate or lithium oxalate or lithium acetate or lithium hydroxide.
The present invention has following advantage and good effect:
Significantly reduce the cost of anode material for lithium-ion batteries, adopt the present invention, because Li 1+ δNi xCo yMn zO 2In rare your resource cobalt only be LiCoO 2In 2%-15%, what replace it is resource than horn of plenty, nickel and manganese that price is lower, the cost of raw material only is LiCoO 2About 1/3, and effectively protected the scarce resource cobalt.Can obtain the equally distributed precursor of nickel cobalt manganese molecular level, adopt the present invention, because nickel cobalt manganese at first is mixed with solution, under the effect of precipitation reagent and complexing agent common deposited takes place then, nickel cobalt manganese reaches the even distribution of molecular level level in the heavy product that forms sediment altogether, helps obtaining forming even, constitutionally stable lithium nickel cobalt manganese oxygen positive electrode.Adopt method of the present invention, can obtain the high density type spherical precursor, help improving the density of lithium nickel cobalt manganese oxygen positive electrode, thereby improve the volume of battery energy density; Technological operation and control are simple.Can improve the specific capacity of anode material for lithium-ion batteries and the energy density of lithium ion battery, with traditional LiCoO 2The work potential scope (2.75-4.3V) of material is compared, lithium nickel cobalt manganese oxygen positive electrode of the present invention can (2.75-4.6V) is reversible in the potential range of broad discharges and recharges, and have higher specific capacity, thereby can obviously improve the energy density of lithium ion battery.
Table 1. adopts the chemical property of the present invention and conventional art lithium ion anode material
Project The * of specific capacity in the half-cell/(mAh/g) The * * of actual specific capacity/(mAh/g)
2.75-4.6V 2.75-4.3V
LiCoO of the present invention 2 >190 - >150 146.8 >140 135.2
In the table: the specific capacity in the * half-cell is to adopt with lithium metal to do the button cell of electrode is tested the gained result;
The * actual specific capacity is for being assembled into actual square lithium ion battery, the result who tests with graphite material between 2.75-4.2V.
Description of drawings
Fig. 1: the XRD analysis collection of illustrative plates of lithium nickel cobalt manganese oxygen material;
Fig. 2: lithium nickel cobalt manganese oxygen is the discharge curve of the lithium ion battery of positive pole;
Fig. 3: lithium nickel cobalt manganese oxygen is the cycle performance curve of the lithium ion battery of positive pole.
Embodiment
1. be raw material with cobalt nitrate, nickelous sulfate, cobaltous sulfate, according to n Ni: n Co: n Mn=0.36: be mixed with 2mol/L (C at 0.08: 0.36 Ni+Co+Mn) mixing salt solution;
Slowly join in the reactor with the ammoniacal liquor of the lithium hydroxide solution of the mixing salt solution of nickel cobalt manganese and 1mol/L, 6mol/L is parallel, hierarchy of control temperature is 50 ± 2 ℃, ammonia concentration is 3.0 ± 0.3g/L, the adding speed control pH value of regulating lithium hydroxide solution is 10.5 ± 0.2, obtains the hydroxide of the nickel cobalt manganese of even codeposition;
The hydroxide of nickel cobalt manganese was handled 6 hours down at 600 ℃ after drying, obtained the composite oxides of nickel cobalt manganese;
Cobalt-nickel-manganese oxide compound and lithium carbonate etc. is pressed atomic ratio n Li: (n XNi+ n Co+ n MnThe mixed of)=1.2: 0.8 is even, ball milling, slowly be warmed up to 950 ℃ after constant temperature 12h, the cooling, fragmentation, classification promptly obtains rich lithium type Li 1.2Ni 0.36Co 0.08Mn 0.36O 2Positive electrode.
To adopting the X-ray diffraction method that the structural analysis (as accompanying drawing 1) of above-mentioned rich lithium type lithium nickel cobalt manganese oxygen is shown that this has α-NaFeO 2The type layer structure.
With above-mentioned with the active material lithium-nickel-cobalt manganese composite oxide, the conductive agent carbon black, binding agent PVDF mixes according to a certain ratio, be coated on the aluminum foil current collector, the oven dry, compressing tablet makes positive plate.
Above-mentioned positive plate and metal lithium sheet are assembled into button cell, discharge and recharge with 20mA/g, recording the reversible capacity of this material between 2.75-4.6V is 196.3mAh/g, and the reversible capacity between 2.75-4.3V is 156.2mAh/g.
Based lithium-ion battery positive plate and barrier film, graphite cathode, electrolyte are assembled square lithium ion battery on industrial production line, discharge and recharge with 0.2C (120mA), the specific capacity that records the lithium nickel cobalt manganese oxygen positive electrode is 143.1mAh/g (as an accompanying drawing 2), is 83.27% (as accompanying drawing 3) with 450 capability retentions afterwards of 0.5C (300mA) cycle charge-discharge.

Claims (4)

1. lithium ion battery anode material lithium nickel cobalt manganese oxygen, it is characterized in that: chemical molecular formula is: Li 1+ δNi xCo yMn zO 2, 1.02<1+ δ<2,0.1<x<0.8,0.02<y<0.15,0.1<z<0.8,0.5<x+y+z<1 wherein.
2. a lithium ion battery anode material lithium nickel cobalt manganese oxygen preparation method is characterized in that: comprise preparation, nickel, cobalt, the co-precipitation of manganese mixing salt solution, the heat treatment of cobalt-nickel-manganese oxide compound;
Adopt the soluble-salt of nickel, cobalt, manganese to make raw material according to n Ni: n Co: n Mn=x: y: z is mixed with nickel, cobalt, the manganese mixing salt solution that concentration is 1-2mol/L, carries out co-precipitation then, and the soluble-salt of nickel, cobalt, manganese comprises sulfate or chloride or acetate;
Co-precipitation is a complexing agent with ammoniacal liquor or ammonium salt, LiOH or KOH or NaOH solution are precipitation reagent, join in the reactor with nickel salt solution, and ammonia concentration is 1g/L-17g/L in the control reaction system, temperature is that 25 ℃-80 ℃, pH value are 9-12, obtains the hydroxide of even codeposition nickel cobalt manganese;
Coprecipitated product is heat-treated at 400 ℃~700 ℃ after drying, obtains the composite oxides of nickel cobalt manganese;
With dried cobalt-nickel-manganese oxide compound is raw material, presses atomic ratio n with Li source compound Li: (n Ni+ n Co+ n Mn=(1+ δ): mixed (x+y+z) is even, ball milling, and after 600 ℃~1000 ℃ high-temperature process, fragmentation, classification promptly gets rich lithium type Li 1+ δNi xCo yMn zO 2Positive electrode.
3. a lithium ion battery anode material lithium nickel cobalt manganese oxygen preparation method is characterized in that: comprise preparation, nickel, cobalt, the co-precipitation of manganese mixing salt solution, the heat treatment of cobalt-nickel-manganese oxide compound;
Adopt the soluble-salt of nickel, cobalt, manganese to make raw material according to n Ni: n Co: n Mn=x: y: z is mixed with nickel, cobalt, the manganese mixing salt solution that concentration is 1-2mol/L, carries out co-precipitation then, and the soluble-salt of nickel, cobalt, manganese comprises sulfate or chloride or acetate;
Co-precipitation is a complexing agent with ammoniacal liquor or ammonium salt, LiOH or KOH or NaOH solution are precipitation reagent, join in the reactor with nickel salt solution, and ammonia concentration is 1g/L-17g/L in the control reaction system, temperature is that 25 ℃-80 ℃, pH value are 9-12, obtains the hydroxide of even codeposition nickel cobalt manganese;
Co-precipitation is made precipitation reagent with oxalic acid or oxalates or carbon dioxide or carbonate or bicarbonate, and the precipitation reagent of excessive 1%-10% and nickel, cobalt, the reaction of manganese mixing salt solution obtain the oxalates or the even codeposit of carbonate of nickel cobalt manganese;
Coprecipitated product is heat-treated at 400 ℃~700 ℃ after drying, obtains the composite oxides of nickel cobalt manganese;
With dried cobalt-nickel-manganese oxide compound is raw material, presses atomic ratio n with Li source compound Li: (n Ni+ n Co+ n Mn)=(1+ δ): mixed (x+y+z) is even, ball milling, and after 600 ℃~1000 ℃ high-temperature process, fragmentation, classification promptly gets rich lithium type Li 1+ δNi xCo yMn zO 2Positive electrode.
4. according to claim 2 or 3 described methods, it is characterized in that: described Li source compound is lithium carbonate or lithium oxalate or lithium acetate or lithium hydroxide.
CNB2005100313543A 2005-03-23 2005-03-23 Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof Expired - Fee Related CN100362681C (en)

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CN101628869A (en) * 2009-08-18 2010-01-20 沈阳张明化工有限公司 Method for preparing cobalt octoate by using LiCoO, anode material of waste lithium battery
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