CN102751485A - Preparation method of composite cathode material for lithium ion battery - Google Patents

Preparation method of composite cathode material for lithium ion battery Download PDF

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CN102751485A
CN102751485A CN201210246394XA CN201210246394A CN102751485A CN 102751485 A CN102751485 A CN 102751485A CN 201210246394X A CN201210246394X A CN 201210246394XA CN 201210246394 A CN201210246394 A CN 201210246394A CN 102751485 A CN102751485 A CN 102751485A
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lithium
cobalt
stratiform
oxide
preparation
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CN102751485B (en
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刘攀
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Cetc Blue Sky Technology Co ltd
Cetc Energy Co ltd
CETC 18 Research Institute
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Abstract

The invention relates to a preparation method of a composite cathode material for a lithium ion battery. The preparation method is characterized by comprising two steps of: preparing a nickel cobalt manganese oxide precursor, and preparing monocrystal layered cobalt lithium oxide grains and polycrystal layered nickel cobalt manganese oxide grains by high-temperature sintering, so that a whole composite cathode material can be grown in a fusing way. Due to the high-temperature sintering, the monocrystal layered cobalt lithium oxide and the polycrystal layered nickel cobalt manganese oxide can be grown into the whole composite cathode material in the fusing way, and the monocrystal layered cobalt lithium oxide grains play a part in supporting, so that the breaking of the material due to rolling of the polycrystal layered nickel cobalt manganese oxide grains can be avoided, and the compacted density of the material can be improved; due to the polycrystal layered nickel cobalt manganese oxide grains, the material is guaranteed to be high in discharge specific capacity and discharge voltage, and the composite cathode material is guaranteed to have the characteristics of being high in energy density, high in discharge voltage and high in compacted density; and by adopting the preparation method, the content of the cobalt element in the cathode material can be reduced, the material cost can be reduced, the preparation method is simple in process, and the preparation method is suitable for large-scale production.

Description

The preparation method of composite anode material for lithium ion battery
Technical field
The invention belongs to the lithium ion battery material technical field, particularly relate to a kind of preparation method of composite anode material for lithium ion battery.
Background technology
Stratiform cobalt-lithium oxide positive electrode is as the founder of anode material for lithium-ion batteries; From 1980 so far; Never be interrupted the exploration to its performance, up to now, the stratiform cobalt-lithium oxide still occupies the market about 85% in the electronic product lithium ion battery; And passed through the development in 30 years, the limit has been attained in the performance of its performance.
Because 3C Product is for the unprecedented demand of energy density; In today that the high-energy-density new material is a dark horse; The defective of stratiform cobalt-lithium oxide aspect energy density unprecedentedly exposes: from gram volume; Because stratiform cobalt-lithium oxide self structure defective, though its theoretical capacity has 275mAh/g, actual reversible specific capacity is generally about 140mAh/g; From the high voltage aspect, the high-pressure electrolysis liquid that common stratiform cobalt-lithium oxide is worked good, 4.3V have been the limit.Though stratiform cobalt nickel oxide manganses lithium anode material has reduced the use amount of rare cobalt element, has reduced cost, between 2.75-4.3V; Reversible specific capacity is more than 160mAh/g; And can bear the above high voltage of 4.3V, but because material self crystallinity problem, stratiform cobalt nickel oxide manganses lithium second particle is in electrode preparation roll-in process; The second particle pattern takes place broken, and compacted density is generally at 3.7g/cm 3Below, cause single stratiform cobalt nickel oxide manganses lithium anode material volume energy density still to be lower than the stratiform cobalt-lithium oxide, though also being stratiform cobalt nickel oxide manganses lithium anode material, this has many advantageous feature, slowly replaced not the main cause of stratiform cobalt-lithium oxide.General technology is that stratiform cobalt-lithium oxide and stratiform cobalt nickel oxide manganses lithium are simply mixed use at present, but this simple physics mixed method exists cost height, discharge voltage and the low deficiency of compacted density.
Summary of the invention
The present invention provides for solving the technical problem that exists in the known technology that a kind of discharge voltage is high, compacted density is high, and the preparation method of the low composite anode material for lithium ion battery of cost.
The present invention for solving the technical scheme that technical problem adopted that exists in the known technology is:
The preparation method of composite anode material for lithium ion battery is characterized in: comprise step 1 and step 2;
Step 1: preparation cobalt nickel oxide manganses presoma:
⑴ adopt the soluble-salt of nickel, cobalt, manganese as nickel, cobalt, manganese source, and being mixed with nickel, cobalt, manganese total ion concentration is the mixed solution of 2-4mol/L; With NaOH is precipitation reagent; Ammoniacal liquor or ammonium salt are as complexing agent; Polyvinyl alcohol, polyethylene glycol, methylcellulose or gelatin are the proportioning of 0.2-0.8 as water soluble dispersing agent with the ammonia alkali mole, in precipitant solution, add complexing agent; Add water soluble dispersing agent again, be prepared into the solution that the preparation of presoma is carried out granularity control; With the solution of mixed solution and granularity control with and stream mode be added to continuously in the stirred autoclave that is connected with inert gas; The flow velocity of agitated reactor is set at 300-500ml/min; Mixing speed is 200-300r/min, and reaction temperature is 45 ℃-85 ℃, and pH value is 8-13; Successive reaction 24-48h forms material;
Employing presoma mixed-sintering method prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2The composite positive pole process:
⑵ carry out Separation of Solid and Liquid with the material that forms among the ⑴ in the press filtration solid-liquid separator, after isolated solid material washs and is 7-8 to pH value, in baking oven, carry out 120-150 ℃, the drying of 10-15h, obtains nickel hydroxide cobalt manganese presoma;
Step 2: that adopts presoma mixed-sintering method, intermediate mixed-sintering method or end product mixed-sintering method a kind ofly prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole;
Said presoma mixed-sintering method comprises following preparation process:
⑴ take by weighing the predecessor and the nickel hydroxide cobalt manganese presoma of stratiform cobalt-lithium oxide with the ratio of the nickel hydroxide cobalt manganese presoma for preparing in the predecessor of stratiform cobalt-lithium oxide and the step 1 according to metal ion total content 20-80:80-20 among both;
⑵ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the lithium source according to the predecessor of the stratiform cobalt-lithium oxide that takes by weighing among the ⑴; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the lithium source according to the nickel hydroxide cobalt manganese presoma that takes by weighing among the ⑴;
⑶ place sintering furnace in 750-1000 ℃ of sintering 5-20 hour after placing a high speed mixer to mix all material that takes by weighing out among ⑴ and the ⑵, behind the stove natural cooling, carries out airflow crash by airslide disintegrating mill, sifts out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, i.e. composite anode material for lithium ion battery;
Said intermediate mixed-sintering method comprises following preparation process:
⑴ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the predecessor and the lithium source of stratiform cobalt-lithium oxide, places a batch mixer to mix, and forms the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the nickel hydroxide cobalt manganese presoma and the lithium source of step 1 preparation, places a batch mixer to mix, and forms the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and place sintering furnace respectively; In 500-850 ℃ of pre-burning 5-15 hour, obtain that the stratiform cobalt-lithium oxide just burns product and stratiform cobalt nickel oxide manganses lithium just burns product;
⑶ according to mass ratio 20-80:80-20; Take by weighing out that ⑵ laminate cobalt-lithium oxide just burns product and stratiform cobalt nickel oxide manganses lithium just burns product; After placing same high speed mixer to mix, place sintering furnace again at 750-1000 ℃ of sintering 5-10 hour, behind the stove natural cooling; Airflow crash sifts out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, i.e. composite anode material for lithium ion battery;
Said end product mixed-sintering method comprises following preparation process:
⑴ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the predecessor and the lithium source of stratiform cobalt-lithium oxide, places a batch mixer to mix, and forms the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the nickel hydroxide cobalt manganese presoma and the lithium source of step 1 preparation, places a batch mixer to mix, and forms the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and place sintering furnace to place sintering furnace respectively respectively; All in 800-1000 ℃ of sintering 5-10 hour; Airflow crash; Through the sub-sieve sub-sieve, obtain stratiform cobalt-lithium oxide LiCoO 2Sintered product and stratiform cobalt nickel oxide manganses lithium Li 1+zMn 1-x-yNi xCo yO 2Sintered product;
⑶ according to the ratio of weight ratio 20-80:80-20, with ⑵ laminate cobalt-lithium oxide LiCoO 2Sintered product and stratiform cobalt nickel oxide manganses lithium Li 1+zMn 1-x-yNi xCo yO 2After sintered product places a high speed mixer to mix, place sintering furnace 350-700 ℃ heat treatment 2-10 hour, behind the stove natural cooling, sift out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, i.e. composite anode material for lithium ion battery.
The present invention can also adopt following technical scheme:
The predecessor of layered cobalt-lithium oxide is one or more in cobalt hydroxide, cobaltosic oxide, cobalt carbonate, cobalt oxalate, cobaltous sulfate, the cobalt chloride;
The soluble-salt of said nickel, cobalt, manganese is one or more in nitrate, sulfate, chlorate, the acetate.
Said lithium source is one or more in lithium carbonate, lithium hydroxide, the lithium acetate.
Said inert gas is a nitrogen.
Said press filtration solid-liquid separator is the washing and filter pressing all-in-one.
Described Li 1+zMn 1-x-yNi xCo yO 2In, 0.05≤z≤0.2,0.1<x≤0.8,1<y≤0.5.
Advantage and good effect that the present invention has are:
1. the present invention makes two kinds of material fusion growth of monocrystalline stratiform cobalt-lithium oxide and polycrystalline stratiform cobalt nickel oxide manganses lithium become as a whole composite positive pole through high temperature sintering; Have micro-Ni, Co, Mn Elements Diffusion layer in two kinds of material granule top layer 1 μ m, grain graininess is between the 7-22 μ m; Monocrystalline cobalt-lithium oxide particle provides support effect; Avoided the fragmentation of polycrystalline stratiform cobalt nickel oxide manganses lithium particle in the roll-in process; Improved the compacted density of material; Polycrystalline stratiform cobalt nickel oxide manganses lithium particle guarantees that material has high specific discharge capacity and discharge voltage, has guaranteed that stratiform cobalt-lithium oxide and stratiform cobalt nickel oxide manganses lithium composite positive pole have the characteristics of high-energy-density, high discharge voltage and high compacted density.
2. the present invention has reduced the content of cobalt element in the positive electrode, reduced material cost, and technology is simple, is convenient to large-scale production.
Description of drawings
Fig. 1 is made into the discharge curve first of 2025 type button cells for the composite positive pole that adopts preparation in the embodiment of the invention 3;
Fig. 2 is the composite positive pole sem photograph of the embodiment of the invention 3 preparations;
Fig. 3 is a monocrystalline stratiform cobalt-lithium oxide sem photograph in the composite positive pole of the embodiment of the invention 3 preparation;
Fig. 4 is a polycrystalline stratiform cobalt nickel oxide manganses lithium sem photograph in the embodiment of the invention 3 preparation composite positive poles.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, the following examples of giving an example now, and conjunction with figs. specifies as follows:
Embodiment 1:
Employing presoma mixed-sintering method prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2The composite positive pole process:
Step 1: preparation cobalt nickel oxide manganses presoma:
⑴ be that to be mixed with nickel, cobalt, manganese total ion concentration be the mixed solution of 3.6mol/L to 5:2:3 with nickelous sulfate, cobaltous sulfate, manganese sulfate according to the Ni:Co:Mn mol ratio; With NaOH as precipitation reagent, ammoniacal liquor as complexing agent, polyethylene glycol as water soluble dispersing agent; It with the ammonia alkali mole 0.3 proportioning; In the sodium hydroxide solution of 12mol/L, add ammoniacal liquor; The polyethylene glycol that adds volume ratio total content 2% again is prepared into the solution that the preparation of presoma is carried out granularity control; With the solution of said mixed solution and said granularity control with and stream mode be added to 170L continuously and be connected with in the stirred autoclave of nitrogen, the flow velocity of agitated reactor is set at 400ml/min, mixing speed is 300r/min; Reaction temperature is 55 ℃; PH value is 12, and successive reaction 24h forms material;
⑵ be transferred to the formation material among the ⑴ and carry out Separation of Solid and Liquid in the washing and filter pressing all-in-one, with isolated solid material wash be 7.5 to pH value after, place baking oven to carry out 120 ℃, the drying of 12h, promptly obtain nickel hydroxide cobalt manganese presoma;
Step 2: preparation LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole:
⑴ with cobalt hydroxide Co (OH) 2With the ratio of the nickel hydroxide cobalt manganese presoma for preparing in the step 1, take by weighing Co (OH) according to metal ion total content 80:20 among both 23720g (40mol) and nickel hydroxide cobalt manganese presoma 916.27g (10mol);
⑵ according to LiCoO 2Component is with the proportioning of mole example Li:Co=1.05, according to the Co that takes by weighing among the ⑴ (OH) 2Weight takes by weighing out lithium carbonate 1554g; According to Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Component, with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.1, the nickel hydroxide cobalt manganese presoma weight according to taking by weighing among the ⑴ takes by weighing out lithium carbonate 407g;
⑶ place a high speed mixer mixing 30min with all material that takes by weighing out among ⑴ and the ⑵; Form mixture; Place sintering furnace in 1000 ℃ of sintering 15 hours in mixture; Behind the stove natural cooling, adopt the MX-50 airslide disintegrating mill broken in 1Mpa air pressure downstream, sift out granularity D through the sub-sieve branch 50The material of=8-20 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole, the discharge capacity of this composite positive pole are 157mAh/g (4.3V), and compacted density is 4.05g/cm 3
Embodiment 2:
Employing intermediate mixed-sintering method prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2The composite positive pole process:
Step 1: identical with the step 1 among the embodiment 1;
Step 2: preparation LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole:
⑴ according to lithium LiCoO 2Component with the proportioning of mole Li:Co=1.05, takes by weighing out cobaltosic oxide Co 3O 4Powder 1070g and lithium carbonate 1165.5g place a batch mixer mixing 30min, form the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.1, takes by weighing nickel hydroxide cobalt manganese presoma 916.27g and lithium carbonate 407g, places a batch mixer mixing 30min, forms the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and respectively place a sintering furnace; All with 800 ℃ of pre-burnings 10 hours, obtain that the stratiform cobalt-lithium oxide just burns product and stratiform cobalt nickel oxide manganses lithium just burns product;
⑶ according to mass ratio 70:30; Take by weighing out that stratiform cobalt-lithium oxide among the ⑵ just burns product and stratiform cobalt nickel oxide manganses lithium just burns product; Place same high speed mixer mixing 30min, placed 1000 ℃ of sintering of sintering furnace again 10 hours, behind the stove natural cooling; Adopt the MX-50 airslide disintegrating mill broken, sift out granularity D through the sub-sieve branch in 1Mpa air pressure downstream 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole, the discharge capacity of this composite positive pole are 160mAh/g (4.3V), 3.96g/cm 3
Embodiment 3:
Employing end product mixed-sintering method prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2The composite positive pole process:
Step 1: identical with the step 1 among the embodiment 1;
Step 2: preparation LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole:
⑴ according to LiCoO 2Component with the proportioning of mole Li:Co=1.05, takes by weighing out cobalt carbonate CoCO 3Powder 1190g and lithium carbonate 388.5g place a batch mixer to mix 30min, form the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Component; Proportioning with mole Li:Me (Me=Ni+Co+Mn)=1.1; Take by weighing out the nickel hydroxide cobalt manganese presoma 916.27g and the lithium carbonate 407g of step 1 preparation, place a batch mixer to mix 30min, form the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and place sintering furnace respectively, all in 1000 ℃ of sintering 10 hours, and air pressure 1Mpa, airflow crash obtains stratiform cobalt-lithium oxide LiCoO 2Sintered product and stratiform cobalt nickel oxide manganses lithium Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Sintered product;
⑶ according to the ratio of weight ratio 50:50, with LiCoO among the ⑵ 2Sintered product and Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Sintered product places a high speed mixer mixing 30min, places 500 ℃ of heat treatments of sintering furnace 8 hours again, behind the stove natural cooling, sifts out granularity D through the sub-sieve branch 50The material of=8-20 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2Composite positive pole, the discharge capacity of this material are 165mAh/g (4.3V), and compacted density is 3.92g/cm 3Fig. 1 is made into the discharge curve first of 2025 type button cells for the composite positive pole that adopts the present embodiment preparation; Fig. 2 is the composite positive pole sem photograph of present embodiment preparation; Fig. 3 is monocrystalline stratiform cobalt-lithium oxide sem photograph in the composite positive pole of present embodiment preparation; Fig. 4 prepares polycrystalline stratiform cobalt nickel oxide manganses lithium sem photograph in the composite positive pole in the present embodiment.
Table 1 is prepared the electrical property comparison of battery for the embodiment of the invention and known technology
LiCoO 2/Li 1.10Ni 0.5Co 0.2Mn 0.3O 2 80：20 70：30 50：50 LiCoO 2 ?Li 1.10Ni 0.5Co 0.2Mn 0.3O 2
Proportioning
Discharge cut-off voltage (V) 4.3 4.3 4.3 4.2 4.3
Discharge capacity (mAh/g) 157 160 165 151 170
Compacted density (g/cm 3) 4.05 3.96 3.92 4.1 3.?6
Can find out that through accompanying drawing and table 1 the composite positive pole compacted density of the present invention's preparation reaches 3.9g/cm 3More than, discharge cut-off voltage reaches 4.3V, reversible discharge capacity>=150mAh/g when discharge-rate is 0.5C, and 600 circulation volume conservation rates are greater than 80%.Characteristics with high-energy-density, high discharge voltage and high compacted density.
Although combine accompanying drawing that the preferred embodiments of the present invention are described above; But the present invention is not limited to above-mentioned embodiment; Above-mentioned embodiment only is schematically, is not restrictive, and those of ordinary skill in the art is under enlightenment of the present invention; Not breaking away under the scope situation that aim of the present invention and claim protect, can also make a lot of forms.These all belong within protection scope of the present invention.

Claims (7)

1. the preparation method of composite anode material for lithium ion battery is characterized in that: comprise step 1 and step 2;
Step 1: preparation cobalt nickel oxide manganses presoma:
⑴ adopt the soluble-salt of nickel, cobalt, manganese as nickel, cobalt, manganese source, and being mixed with nickel, cobalt, manganese total ion concentration is the mixed solution of 2-4mol/L; With NaOH is precipitation reagent; Ammoniacal liquor or ammonium salt are as complexing agent; Polyvinyl alcohol, polyethylene glycol, methylcellulose or gelatin are the proportioning of 0.2-0.8 as water soluble dispersing agent with the ammonia alkali mole, in precipitant solution, add complexing agent; Add water soluble dispersing agent again, be prepared into the solution that the preparation of presoma is carried out granularity control; With the solution of mixed solution and granularity control with and stream mode be added to continuously in the stirred autoclave that is connected with inert gas; The flow velocity of agitated reactor is set at 300-500ml/min; Mixing speed is 200-300r/min, and reaction temperature is 45 ℃-85 ℃, and pH value is 8-13; Successive reaction 24-48h forms material;
Employing presoma mixed-sintering method prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole LiCoO 2/ Li 1.10Ni 0.5Co 0.2Mn 0.3O 2The composite positive pole process:
⑵ carry out Separation of Solid and Liquid with the material that forms among the ⑴ in the press filtration solid-liquid separator, after isolated solid material washs and is 7-8 to pH value, in baking oven, carry out 120-150 ℃, the drying of 10-15h, obtains nickel hydroxide cobalt manganese presoma;
Step 2: that adopts presoma mixed-sintering method, intermediate mixed-sintering method or end product mixed-sintering method a kind ofly prepares monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole;
Said presoma mixed-sintering method comprises following preparation process:
⑴ take by weighing the predecessor and the nickel hydroxide cobalt manganese presoma of stratiform cobalt-lithium oxide with the ratio of the nickel hydroxide cobalt manganese presoma for preparing in the predecessor of stratiform cobalt-lithium oxide and the step 1 according to metal ion total content 20-80:80-20 among both;
⑵ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the lithium source according to the predecessor of the stratiform cobalt-lithium oxide that takes by weighing among the ⑴; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the lithium source according to the nickel hydroxide cobalt manganese presoma that takes by weighing among the ⑴;
⑶ place sintering furnace in 750-1000 ℃ of sintering 5-20 hour after placing a high speed mixer to mix all material that takes by weighing out among ⑴ and the ⑵, behind the stove natural cooling, carries out airflow crash by airslide disintegrating mill, sifts out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, composite anode material for lithium ion battery promptly of the present invention;
Said intermediate mixed-sintering method comprises following preparation process:
⑴ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the predecessor and the lithium source of stratiform cobalt-lithium oxide, places a batch mixer to mix, and forms the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the nickel hydroxide cobalt manganese presoma and the lithium source of step 1 preparation, places a batch mixer to mix, and forms the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and place sintering furnace respectively; In 500-850 ℃ of pre-burning 5-15 hour, obtain that the stratiform cobalt-lithium oxide just burns product and stratiform cobalt nickel oxide manganses lithium just burns product;
⑶ according to mass ratio 20-80:80-20; Take by weighing out that ⑵ laminate cobalt-lithium oxide just burns product and stratiform cobalt nickel oxide manganses lithium just burns product; After placing same high speed mixer to mix, place sintering furnace again at 750-1000 ℃ of sintering 5-10 hour, behind the stove natural cooling; Airflow crash sifts out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, composite anode material for lithium ion battery promptly of the present invention;
Said end product mixed-sintering method comprises following preparation process:
⑴ according to LiCoO 2Component with the proportioning of mole Li:Co=1-1.05, takes by weighing out the predecessor and the lithium source of stratiform cobalt-lithium oxide, places a batch mixer to mix, and forms the mixture after stratiform cobalt-lithium oxide predecessor is joined lithium; According to Li 1+zMn 1-x-yNi xCo yO 2Component with the proportioning of mole Li:Me (Me=Ni+Co+Mn)=1.05-1.2, takes by weighing out the nickel hydroxide cobalt manganese presoma and the lithium source of step 1 preparation, places a batch mixer to mix, and forms the mixture after nickel hydroxide cobalt manganese presoma is joined lithium;
⑵ join the mixture that mixture and nickel hydroxide cobalt manganese presoma behind the lithium join behind the lithium with ⑴ laminate cobalt-lithium oxide predecessor and place sintering furnace to place sintering furnace respectively respectively; All in 800-1000 ℃ of sintering 5-10 hour; Airflow crash; Through the sub-sieve sub-sieve, obtain stratiform cobalt-lithium oxide LiCoO 2Sintered product and stratiform cobalt nickel oxide manganses lithium Li 1+zMn 1-x-yNi xCo yO 2Sintered product;
⑶ according to the ratio of weight ratio 20-80:80-20, with ⑵ laminate cobalt-lithium oxide LiCoO 2Sintered product and stratiform cobalt nickel oxide manganses lithium Li 1+zMn 1-x-yNi xCo yO 2After sintered product places a high speed mixer to mix, place sintering furnace 350-700 ℃ heat treatment 2-10 hour, behind the stove natural cooling, sift out granularity D through the sub-sieve branch 50The material of=7-25 μ m is monocrystalline stratiform cobalt-lithium oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole, composite anode material for lithium ion battery promptly of the present invention.
2. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: the predecessor of layered cobalt-lithium oxide is one or more in cobalt hydroxide, cobaltosic oxide, cobalt carbonate, cobalt oxalate, cobaltous sulfate, the cobalt chloride.
3. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: the soluble-salt of said nickel, cobalt, manganese is one or more in nitrate, sulfate, chlorate, the acetate.
4. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: said lithium source is one or more in lithium carbonate, lithium hydroxide, the lithium acetate.
5. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: said inert gas is a nitrogen.
6. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: said press filtration solid-liquid separator is the washing and filter pressing all-in-one.
7. according to the preparation method of the said composite anode material for lithium ion battery of claim 1, it is characterized in that: described Li 1+zMn 1-x-yNi xCo yO 2In, 0.05≤z≤0.2,0.1<x≤0.8,1<y≤0.5.
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