CN102751485B - The preparation method of composite anode material for lithium ion battery - Google Patents
The preparation method of composite anode material for lithium ion battery Download PDFInfo
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- CN102751485B CN102751485B CN201210246394.XA CN201210246394A CN102751485B CN 102751485 B CN102751485 B CN 102751485B CN 201210246394 A CN201210246394 A CN 201210246394A CN 102751485 B CN102751485 B CN 102751485B
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Abstract
The present invention relates to a kind of preparation method of composite anode material for lithium ion battery, be characterized in: comprise two large steps: prepare nickel hydroxide cobalt manganese presoma and high temperature sintering prepares monocrystalline layered lithium cobalt oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole.The present invention is owing to passing through high temperature sintering, monocrystalline layered lithium cobalt oxide is made to become as a whole composite positive pole with polycrystalline stratiform cobalt nickel oxide manganses lithium bi-material fusion growth, monocrystalline cobalt-lithium oxide particle plays a supportive role, avoid the fragmentation of polycrystalline stratiform cobalt nickel oxide manganses lithium particle roll-in, improve the compacted density of material; Polycrystalline stratiform cobalt nickel oxide manganses lithium particle ensures that material has high specific discharge capacity and discharge voltage, ensure that composite positive pole has the feature of high-energy-density, high discharge voltage and high compacted density; Present invention reduces the content of cobalt element in positive electrode, reduce material cost, and technique is simple, is convenient to large-scale production.
Description
Technical field
The invention belongs to lithium ion battery material technical field, particularly relate to a kind of preparation method of composite anode material for lithium ion battery.
Background technology
Layered lithium cobalt 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, layered lithium cobalt oxide still occupies the market of about 85% in electronic product lithium ion battery, and have passed through the development of 30 years, the performance of its performance attains the limit.
Because 3C Product is for the Unprecedented demands of energy density, in today that high-energy-density new material is a dark horse, the defect of layered lithium cobalt oxide in energy density unprecedentedly exposes: from gram volume, due to layered lithium cobalt oxide self structure defect, although its theoretical capacity has 275mAh/g, actual reversible specific capacity is generally at about 140mAh/g; From the viewpoint of high voltage, the high-voltage electrolyte that common layered lithium cobalt oxide is worked good, 4.3V has been the limit.Although stratiform cobalt nickel oxide manganses lithium anode material decreases the use amount of rare cobalt element, reduce cost, between 2.75-4.3V, reversible specific capacity is at more than 160mAh/g, and more than 4.3V high voltage can be born, but due to material self crystallinity problem, stratiform cobalt nickel oxide manganses lithium second particle is prepared in nipping process at electrode, second particle pattern occurs 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 lower than layered lithium cobalt oxide, although this is also stratiform cobalt nickel oxide manganses lithium anode material have many advantages feature, slowly do not replace the main cause of layered lithium cobalt oxide.Technique general be at present by layered lithium cobalt oxide and stratiform cobalt nickel oxide manganses lithium simply used in combination, but this simple physical mixing processes exists that cost is high, discharge voltage and the low deficiency of compacted density.
Summary of the invention
The present invention provides that a kind of discharge voltage is high, compacted density is high for solving in known technology the technical problem that exists, and the preparation method of the low composite anode material for lithium ion battery of cost.
The technical scheme that the present invention adopts for the technical problem existed in solution known technology is:
The preparation method of composite anode material for lithium ion battery, is characterized in: comprise step one and step 2;
Step one: prepare nickel hydroxide cobalt manganese presoma:
(1) adopt the soluble-salt of nickel, cobalt, manganese as nickel, cobalt, manganese source, be mixed with nickel, cobalt, manganese total ion concentration be the mixed solution of 2-4mol/L; Take NaOH as precipitation reagent, ammoniacal liquor or ammonium salt are as complexing agent, polyvinyl alcohol, polyethylene glycol, methylcellulose or gelatin are as water soluble dispersing agent, with the proportioning that ammonia alkali mole is 0.2-0.8, complexing agent is added in precipitant solution, add water soluble dispersing agent again, be prepared into the solution preparation of presoma being carried out to Task-size Controlling; By the solution of mixed solution and Task-size Controlling with and the mode that flows be added to continuously and be connected with in the stirred autoclave of nitrogen, the flow rate set of reactor is 300-500ml/min, mixing speed is 200-300r/min, reaction temperature is 45 DEG C-85 DEG C, pH value is 8-13, successive reaction 24-48h, forms material;
(2) the material formed in is (1) carried out Separation of Solid and Liquid in press filtration solid-liquid separator, after isolated solid material washing is 7-8 to pH value, carries out 120-150 DEG C, the drying of 10-15h in an oven, obtain nickel hydroxide cobalt manganese presoma;
Step 2: what adopt presoma mixed-sintering method, intermediate mixed-sintering method or end product mixed-sintering method a kind ofly prepares monocrystalline layered lithium cobalt oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole;
Described presoma mixed-sintering method comprises following preparation process:
By the nickel hydroxide cobalt manganese presoma prepared in the predecessor of layered lithium cobalt oxide and step one according to the ratio of metal ion total content mol ratio 20-80:80-20 in both, take predecessor and the nickel hydroxide cobalt manganese presoma of layered lithium cobalt oxide;
(2) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, the predecessor according to the layered lithium cobalt oxide taken in (1) takes out lithium source; 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, the nickel hydroxide cobalt manganese presoma according to taking in (1) takes out lithium source;
(3) all material taken out in (1) and is (2) placed in after a high speed mixer mixes, is placed in sintering furnace in 750-1000 DEG C of sintering 5-20 hour, after naturally cooling with stove, carries out airflow crash by airslide disintegrating mill, divided by sub-sieve and sift out granularity D
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention; Complete and adopt presoma mixed-sintering method to prepare monocrystalline layered lithium cobalt 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 process;
Described intermediate mixed-sintering method comprises following preparation process:
(1) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, takes out predecessor and the lithium source of layered lithium cobalt oxide, is placed in a batch mixer and mixes, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take out nickel hydroxide cobalt manganese presoma and the lithium source of step one preparation, be placed in a batch mixer and mix, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be placed in sintering furnace respectively, in 500-850 DEG C of pre-burning 5-15 hour, obtain layered lithium cobalt oxide and just burn product and stratiform cobalt nickel oxide manganses lithium just burns product;
(3) according to mass ratio 20-80:80-20, take out (2) laminate cobalt-lithium oxide and just burn product and stratiform cobalt nickel oxide manganses lithium just burns product, be placed in after same high speed mixer mix, be placed in sintering furnace again at 750-1000 DEG C of sintering 5-10 hour, naturally after cooling with stove, airflow crash, is divided by sub-sieve and sifts out granularity D
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention;
Described end product mixed-sintering method comprises following preparation process:
(1) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, takes out predecessor and the lithium source of layered lithium cobalt oxide, is placed in a batch mixer and mixes, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take out nickel hydroxide cobalt manganese presoma and the lithium source of step one preparation, be placed in a batch mixer and mix, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be placed in sintering furnace respectively, all in 800-1000 DEG C of sintering 5-10 hour, airflow crash, by sub-sieve sub-sieve, obtains layered lithium cobalt oxide LiCoO
2sintered product and stratiform cobalt nickel oxide manganses lithium Li
1+zmn
1-x-yni
xco
yo
2sintered product;
(3), according to the ratio of weight ratio 20-80:80-20, incite somebody to action (2) laminate cobalt-lithium oxide LiCoO
2sintered product and stratiform cobalt nickel oxide manganses lithium Li
1+zmn
1-x-yni
xco
yo
2sintered product is placed in after a high speed mixer mixes, and is placed in sintering furnace 350-700 DEG C of heat treatment 2-10 hour, after naturally cooling, is divided sift out granularity D by sub-sieve with stove
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention.
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, cobalt chloride;
The soluble-salt of described nickel, cobalt, manganese is one or more in nitrate, sulfate, chlorate, acetate.
Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate.
Described press filtration solid-liquid separator is washing and filter pressing all-in-one.
The advantage that the present invention has and good effect are:
1. the present invention makes monocrystalline layered lithium cobalt oxide become as a whole composite positive pole with polycrystalline stratiform cobalt nickel oxide manganses lithium bi-material fusion growth by high temperature sintering, there is Ni, Co, Mn Elements Diffusion layer of trace in 1 μm, bi-material particle top layer, grain graininess is between 7-22 μm; Monocrystalline cobalt-lithium oxide particle provides a supporting role, avoid the fragmentation of polycrystalline stratiform cobalt nickel oxide manganses lithium particle in nipping process, improve the compacted density of material, polycrystalline stratiform cobalt nickel oxide manganses lithium particle ensures that material has high specific discharge capacity and discharge voltage, ensure that layered lithium cobalt oxide and stratiform cobalt nickel oxide manganses lithium composite positive pole have the feature of high-energy-density, high discharge voltage and high compacted density.
2. present invention reduces the content of cobalt element in positive electrode, reduce material cost, and technique is simple, is convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is the discharge curve first adopting the composite positive pole of preparation in the embodiment of the present invention 3 to be made into 2025 type button cells;
Fig. 2 is composite positive pole scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 3;
Fig. 3 is monocrystalline layered lithium cobalt oxide scanning electron microscope (SEM) photograph in the composite positive pole of the embodiment of the present invention 3 preparation;
Fig. 4 is that the embodiment of the present invention 3 prepares polycrystalline stratiform cobalt nickel oxide manganses lithium scanning electron microscope (SEM) photograph in composite positive pole.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Embodiment 1:
Employing presoma mixed-sintering method prepares monocrystalline layered lithium cobalt 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 process:
Step one: prepare nickel hydroxide cobalt manganese presoma:
(1) be that 5:2:3 is mixed with nickel, cobalt, manganese total ion concentration are the mixed solution of 3.6mol/L by nickelous sulfate, cobaltous sulfate, manganese sulfate according to Ni:Co:Mn mol ratio; Using NaOH as precipitation reagent, ammoniacal liquor is as complexing agent, polyethylene glycol as water soluble dispersing agent, be the proportioning of 0.3 with ammonia alkali mole, ammoniacal liquor is added in the sodium hydroxide solution of 12mol/L, add the polyethylene glycol of volume ratio total content 2% again, be prepared into the solution preparation of presoma being carried out to Task-size Controlling; By the solution of described mixed solution and described Task-size Controlling with and the mode that flows is added to 170L is continuously connected with in the stirred autoclave of nitrogen, the flow rate set of reactor is 400ml/min, and mixing speed is 300r/min, reaction temperature is 55 DEG C, pH value is 12, successive reaction 24h, forms material;
(2) being transferred in washing and filter pressing all-in-one by the formation material in (1) and carrying out Separation of Solid and Liquid, is after 7.5 by isolated solid material washing to pH value, is placed in baking oven and carries out 120 DEG C, the drying of 12h, namely obtain nickel hydroxide cobalt manganese presoma;
Step 2: preparation LiCoO
2/ Li
1.10ni
0.5co
0.2mn
0.3o
2composite positive pole:
(1) by cobalt hydroxide Co (OH)
2with the nickel hydroxide cobalt manganese presoma prepared in step one according to the ratio of metal ion total content 80:20 in both, take Co (OH)
23720g (40mol) and nickel hydroxide cobalt manganese presoma 916.27g (10mol);
(2) according to LiCoO
2component, with the proportioning of mole example Li:Co=1.05, according to the Co (OH) taken in (1)
2weight, takes 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, according to the nickel hydroxide cobalt manganese presoma weight taken in (1), takes out lithium carbonate 407g;
(3) all material taken out in (1) and is (2) placed in a high speed mixer mixing 30min, form mixture, mixture is placed in sintering furnace and sinters 15 hours in 1000 DEG C, naturally after cooling with stove, adopt MX-50 airslide disintegrating mill broken in 1Mpa air pressure downstream, divided by sub-sieve and sift out granularity D
50the material of=8-20 μm, is monocrystalline layered lithium cobalt 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 is 157mAh/g (4.3V), and compacted density is 4.05g/cm
3.
Embodiment 2:
Employing intermediate mixed-sintering method prepares monocrystalline layered lithium cobalt 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 process:
Step one: identical with the step one in embodiment 1;
Step 2: preparation LiCoO
2/ Li
1.10ni
0.5co
0.2mn
0.3o
2composite positive pole:
(1) according to lithium LiCoO
2component, with the proportioning of mole Li:Co=1.05, takes out cobaltosic oxide Co
3o
4powder 1070g and lithium carbonate 1165.5g, is placed in a batch mixer mixing 30min, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take nickel hydroxide cobalt manganese presoma 916.27g and lithium carbonate 407g, be placed in a batch mixer mixing 30min, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be respectively placed in a sintering furnace, all with 800 DEG C of pre-burnings 10 hours, obtain layered lithium cobalt oxide and just burn product and stratiform cobalt nickel oxide manganses lithium just burns product;
(3) according to mass ratio 70:30, the layered lithium cobalt oxide taken out (2) just burns product and stratiform cobalt nickel oxide manganses lithium just burns product, be placed in same high speed mixer mixing 30min, be placed in sintering furnace 1000 DEG C sintering again 10 hours, naturally after cooling with stove, adopt MX-50 airslide disintegrating mill broken in 1Mpa air pressure downstream, divided by sub-sieve and sift out granularity D
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 is 160mAh/g (4.3V), 3.96g/cm
3.
Embodiment 3:
Employing end product mixed-sintering method prepares monocrystalline layered lithium cobalt 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 process:
Step one: identical with the step one in embodiment 1;
Step 2: preparation LiCoO
2/ Li
1.10ni
0.5co
0.2mn
0.3o
2composite positive pole:
(1) according to LiCoO
2component, with the proportioning of mole Li:Co=1.05, takes out cobalt carbonate CoCO
3powder 1190g and lithium carbonate 388.5g, is placed in a batch mixer and mixes 30min, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take out nickel hydroxide cobalt manganese presoma 916.27g and the lithium carbonate 407g of step one preparation, be placed in a batch mixer and mix 30min, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be placed in sintering furnace respectively, all in 1000 DEG C of sintering 10 hours, air pressure 1Mpa, airflow crash, obtains layered lithium cobalt oxide LiCoO
2sintered product and stratiform cobalt nickel oxide manganses lithium Li
1.10ni
0.5co
0.2mn
0.3o
2sintered product;
(3), according to the ratio of weight ratio 50:50, incite somebody to action LiCoO (2)
2sintered product and Li
1.10ni
0.5co
0.2mn
0.3o
2sintered product is placed in a high speed mixer mixing 30min, then is placed in sintering furnace 500 DEG C of heat treatments 8 hours, after naturally cooling, is divided sift out granularity D by sub-sieve with stove
50the material of=8-20 μm, is monocrystalline layered lithium cobalt 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 is 165mAh/g (4.3V), and compacted density is 3.92g/cm
3.Fig. 1 is the discharge curve first that the composite positive pole adopting the present embodiment to prepare is made into 2025 type button cells; Fig. 2 is composite positive pole scanning electron microscope (SEM) photograph prepared by the present embodiment; Fig. 3 is monocrystalline layered lithium cobalt oxide scanning electron microscope (SEM) photograph in the composite positive pole prepared of the present embodiment; Fig. 4 prepares polycrystalline stratiform cobalt nickel oxide manganses lithium scanning electron microscope (SEM) photograph in composite positive pole in the present embodiment.
Table 1 compares with the electrical property that known technology prepares battery for the embodiment of the present invention
Can be found out by accompanying drawing and table 1, composite positive pole compacted density prepared by the present invention reaches 3.9g/cm
3above, discharge cut-off voltage reaches 4.3V, reversible discharge capacity>=150mAh/g when discharge-rate is 0.5C, and 600 times circulation volume conservation rate is greater than 80%.There is the feature of high-energy-density, high discharge voltage and high compacted density.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (5)
1. the preparation method of composite anode material for lithium ion battery, is characterized in that: comprise step one and step 2;
Step one: prepare nickel hydroxide cobalt manganese presoma:
(1) adopt the soluble-salt of nickel, cobalt, manganese as nickel, cobalt, manganese source, be mixed with nickel, cobalt, manganese total ion concentration be the mixed solution of 2-4mol/L; Take NaOH as precipitation reagent, ammoniacal liquor or ammonium salt are as complexing agent, polyvinyl alcohol, polyethylene glycol, methylcellulose or gelatin are as water soluble dispersing agent, with the proportioning that ammonia alkali mole is 0.2-0.8, complexing agent is added in precipitant solution, add water soluble dispersing agent again, be prepared into the solution preparation of presoma being carried out to Task-size Controlling; By the solution of mixed solution and Task-size Controlling with and the mode that flows be added to continuously and be connected with in the stirred autoclave of nitrogen, the flow rate set of reactor is 300-500ml/min, mixing speed is 200-300r/min, reaction temperature is 45 DEG C-85 DEG C, pH value is 8-13, successive reaction 24-48h, forms material;
(2) the material formed in is (1) carried out Separation of Solid and Liquid in press filtration solid-liquid separator, after isolated solid material washing is 7-8 to pH value, carries out 120-150 DEG C, the drying of 10-15h in an oven, obtain nickel hydroxide cobalt manganese presoma;
Step 2: what adopt presoma mixed-sintering method, intermediate mixed-sintering method or end product mixed-sintering method a kind ofly prepares monocrystalline layered lithium cobalt oxide particle and polycrystalline stratiform cobalt nickel oxide manganses lithium particles coalesce grows into as a whole composite positive pole;
Described presoma mixed-sintering method comprises following preparation process:
By the nickel hydroxide cobalt manganese presoma prepared in the predecessor of layered lithium cobalt oxide and step one according to the ratio of metal ion total content mol ratio 20-80:80-20 in both, take predecessor and the nickel hydroxide cobalt manganese presoma of layered lithium cobalt oxide;
(2) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, the predecessor according to the layered lithium cobalt oxide taken in (1) takes out lithium source; 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, the nickel hydroxide cobalt manganese presoma according to taking in (1) takes out lithium source;
(3) all material taken out in (1) and is (2) placed in after a high speed mixer mixes, is placed in sintering furnace in 750-1000 DEG C of sintering 5-20 hour, after naturally cooling with stove, carries out airflow crash by airslide disintegrating mill, divided by sub-sieve and sift out granularity D
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention; Complete and adopt presoma mixed-sintering method to prepare monocrystalline layered lithium cobalt 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 process;
Described intermediate mixed-sintering method comprises following preparation process:
(1) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, takes out predecessor and the lithium source of layered lithium cobalt oxide, is placed in a batch mixer and mixes, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take out nickel hydroxide cobalt manganese presoma and the lithium source of step one preparation, be placed in a batch mixer and mix, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be placed in sintering furnace respectively, in 500-850 DEG C of pre-burning 5-15 hour, obtain layered lithium cobalt oxide and just burn product and stratiform cobalt nickel oxide manganses lithium just burns product;
(3) according to mass ratio 20-80:80-20, take out (2) laminate cobalt-lithium oxide and just burn product and stratiform cobalt nickel oxide manganses lithium just burns product, be placed in after same high speed mixer mix, be placed in sintering furnace again at 750-1000 DEG C of sintering 5-10 hour, naturally after cooling with stove, airflow crash, is divided by sub-sieve and sifts out granularity D
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention;
Described end product mixed-sintering method comprises following preparation process:
(1) according to LiCoO
2component, with the proportioning of mole Li:Co=1-1.05, takes out predecessor and the lithium source of layered lithium cobalt oxide, is placed in a batch mixer and mixes, and formation layered lithium cobalt oxide predecessor joins the mixture after 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, take out nickel hydroxide cobalt manganese presoma and the lithium source of step one preparation, be placed in a batch mixer and mix, formation nickel hydroxide cobalt manganese presoma joins the mixture after lithium;
(2) (1) laminate cobalt-lithium oxide predecessor is joined the mixture after lithium and nickel hydroxide cobalt manganese presoma to join the mixture after lithium and be placed in sintering furnace respectively, all in 800-1000 DEG C of sintering 5-10 hour, airflow crash, by sub-sieve sub-sieve, obtains layered lithium cobalt oxide LiCoO
2sintered product and stratiform cobalt nickel oxide manganses lithium Li
1+zmn
1-x-yni
xco
yo
2sintered product;
(3), according to the ratio of weight ratio 20-80:80-20, incite somebody to action (2) laminate cobalt-lithium oxide LiCoO
2sintered product and stratiform cobalt nickel oxide manganses lithium Li
1+zmn
1-x-yni
xco
yo
2sintered product is placed in after a high speed mixer mixes, and is placed in sintering furnace 350-700 DEG C of heat treatment 2-10 hour, after naturally cooling, is divided sift out granularity D by sub-sieve with stove
50the material of=7-25 μm, is monocrystalline layered lithium cobalt 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 of the present invention.
2. the preparation method of composite anode material for lithium ion battery according to claim 1, 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, cobalt chloride.
3. the preparation method of composite anode material for lithium ion battery according to claim 1, is characterized in that: the soluble-salt of described nickel, cobalt, manganese is one or more in nitrate, sulfate, chlorate, acetate.
4. the preparation method of composite anode material for lithium ion battery according to claim 1, is characterized in that: described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate.
5. the preparation method of composite anode material for lithium ion battery according to claim 1, is characterized in that: described press filtration solid-liquid separator is washing and filter pressing all-in-one.
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|---|---|---|---|
| CN201210246394.XA CN102751485B (en) | 2012-07-17 | 2012-07-17 | The preparation method of composite anode material for lithium ion battery |
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|---|---|---|---|
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