CN108417790A - A kind of anode material for lithium-ion batteries and its preparation method and application - Google Patents
A kind of anode material for lithium-ion batteries and its preparation method and application Download PDFInfo
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- CN108417790A CN108417790A CN201810088934.3A CN201810088934A CN108417790A CN 108417790 A CN108417790 A CN 108417790A CN 201810088934 A CN201810088934 A CN 201810088934A CN 108417790 A CN108417790 A CN 108417790A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries includes the interior nuclear phase layer containing ternary nickel, cobalt and manganese oxide and containing the surface coating layer of lithium chromate.The invention also discloses a kind of preparation method and application of anode material for lithium-ion batteries.Anode material for lithium-ion batteries of the present invention has coated one layer of lithium chromate on the basis of nickel-cobalt-manganternary ternary anode material, and clad can effectively inhibit the side reaction between material and electrolyte, greatly improve the cycle performance and security performance of material.The anode material for lithium-ion batteries of the present invention has high circulation performance and high safety performance, can also improve the specific capacity of electrode.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of anode material for lithium-ion batteries and its preparation side
Method and application.
Background technology
Energy crisis is the great development problem that the whole world faces jointly now, it hinders human society industrial Information
Further development, so it forces people to look for the new green energy resource that can be recycled.In the 1980s, lithium
Ion battery comes into being.Compare for traditional lead acid batteries, nickel-cadmium cell and Ni-MH battery, it have high discharge voltage,
Outstanding advantages of high power capacity, memory-less effect, small, excellent cyclicity, so having received widespread attention and quickly growing.
And with the continuous development of lithium ion battery, its application field also becomes larger, and includes not only mobile phone, notebook electricity
The civil fields such as brain, video camera, digital camera, have also gradually been related to military field.Now, both at home and abroad all in research large capacity
In lithium ion battery applications to the industries such as electric vehicle, space flight and energy storage.Anode material for lithium-ion batteries as influence lithium from
The most important factor that sub- battery entirety chemical property plays, the bottleneck of its development bottleneck i.e. lithium ion battery development.
So having the system of the lithium ion anode material of high-energy density, high working voltage, good cycle performance and security performance each and answering
With becoming global focus of attention.
Li[Ni,Co,Mn]O2Series material abbreviation ternary material has preferably had both lithium cobalt oxide, lithium nickel oxygen, lithium manganese oxygen
Advantage, and respective deficiency is compensated for a certain extent, there is height ratio capacity, stable cycle performance, advantage of lower cost, peace
The features such as full better performances.By introducing cobalt, cation mixing occupancy, the stratiform knot of effective stabilizing material can be reduced
Structure；By introducing manganese, the capacity of material can be improved by introducing, can not only reduce material cost, but also material can be improved
The safety and stability of material.Therefore, which is considered as that can replace LiCoO2Best positive electrode.
Li[Ni,Co,Mn]O2Good physical behavior and chemical property so that at it in portable power lithium electricity side
Face, which becomes, substitutes LiCoO2Optimal material, but Li [Ni, Co, Mn] O2High rate capability be not highly desirable, hinder
Its application in mixed type electrical source of power, this is mainly related with the electronic conductivity of material.In addition the material is in high charge-discharge
Under voltage, cyclical stability is poor.
Invention content
Technical problems based on background technology, the present invention propose a kind of anode material for lithium-ion batteries and its preparation
Methods and applications, anode material for lithium-ion batteries of the invention have high circulation performance and high safety performance, can also improve electricity
The specific capacity of pole.
The present invention proposes a kind of anode material for lithium-ion batteries, and the anode material for lithium-ion batteries includes containing ternary
The interior nuclear phase layer of nickel, cobalt and manganese oxide and the surface coating layer containing lithium chromate.
Preferably, the chemical formula of the anode material for lithium-ion batteries is LixNiaCobMncCrdO2, wherein 1≤x≤
L.07,0<a<L, 0<b<1,0<c<1,0.01≤d≤0.10, and a+b+c+d=1.
Preferably, in chemical formula, 0.02≤d≤0.04.
Preferably, the thickness of the surface coating layer containing lithium chromate is 10-100nm.
The present invention also proposes a kind of preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, the sulfide solution of nickel, cobalt, manganese is hybridly prepared into mixed solution, then by mixed solution, NaOH solution,
Ammonia spirit is mixed, and sediment is obtained after reacting, and sediment is filtered, is dry, then in the case where being sintered atmosphere,
Ternary precursor is sintered, nickel cobalt manganese hydroxide, i.e. ternary precursor are obtained；
S2, by lithium source, sintered ternary precursor mixing and ball milling, obtain mixed powder, then carry out mixed powder
Nickel-cobalt-manganese ternary material is obtained after sintering；
S3, nickel-cobalt-manganese ternary material, lithium chromate are mixed, then calcine, obtains the nickel cobalt manganese three of cladding lithium chromate
First material is to get to anode material for lithium-ion batteries.
Preferably, in S1, control ph is 10.0-12.0 in mixing process.
Preferably, in S1, control ph is 10.4-11.6 in mixing process.
Preferably, in S1, reaction temperature is 40-70 DEG C.
Preferably, in S1, the sintering gas is selected from least one of oxygen, air, compressed air.
Preferably, in S1, the flow for being sintered gas is 0.l-1.5L/min/kg.
Preferably, in S1, the temperature of sintering is 450-700 DEG C, time 4-8h.
Preferably, in S1, the temperature of sintering is 600 DEG C, time 6h.
Preferably, in S2, lithium source be selected from the oxide of lithium, halide, hydroxide, carbonate, nitrate, acetate,
At least one of oxalates.
Preferably, in S2, the molar ratio of ternary precursor and elemental lithium is 1：1-1.07.
Preferably, in S2, the condition of the sintering is first to be sintered 3-10h at 450-700 DEG C in the case where being sintered atmosphere
After rise at 650-1000 DEG C and be sintered 8-20h.
Preferably, in S2, the condition of the sintering is to be risen to after being first sintered 6h at 500 DEG C in the case where being sintered atmosphere
It is sintered 10h at 850 DEG C.
Preferably, the sintering gas is selected from least one of oxygen, air, compressed air.
Preferably, the gas flow of the sintering gas is 0.l-1.5L/min/kg.
Preferably, in S3, the lithium chromate is selected from Li2CrO4·2H2O、Li2CrO4At least one of.
Preferably, in S3, the molar ratio of the nickel-cobalt-manganese ternary material and lithium chromate is 1：0.02-0.08.
Preferably, in S3, the molar ratio of the nickel-cobalt-manganese ternary material and lithium chromate is 1：0.02-0.04.
Preferably, in S3, the time of the stirring is 0.5-2h.
Preferably, in S3, the temperature of the calcining is 450-700 DEG C, calcination time 2-10h.
Preferably, in S3, the temperature of the calcining is 550 DEG C, calcination time 6h.
A kind of lithium ion battery, including shell, the anode being placed in shell, cathode, diaphragm and electrolyte, diaphragm are located at institute
It states between anode and cathode, the anode includes above-mentioned anode material for lithium-ion batteries.
Compared with prior art, beneficial effects of the present invention are as follows：
1) anode material for lithium-ion batteries of the invention has high circulation performance and high safety performance, can also improve electrode
Specific capacity.The present invention has coated one layer of lithium chromate after prepared by nickel-cobalt-manganternary ternary anode material, and clad can effectively press down
Side reaction between prepared material and electrolyte greatly improves the cycle performance and security performance of material.
2) present invention is the anode material for lithium-ion batteries with high power charging-discharging.Coating layer material contains in the present invention
Lithium ion can not only prevent positive electrode to be in direct contact generation side reaction with electrolyte, and make positive electrode and electrolysis
There is higher ionic conductivity, to reduce impedance, the high rate performance of material is also opposite to be improved between the reaction interface of liquid
It is many.In addition, chromium ion is aoxidized simultaneously in charging process in clad, the specific discharge capacity of material further can obtain
Cladding to raising, chromium ion also makes moderate progress for the high rate performance of material.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries include containing ternary nickel, cobalt and manganese oxide
Interior nuclear phase layer and the surface coating layer containing lithium chromate.
The preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, the sulfide solution of nickel, cobalt, manganese is hybridly prepared into mixed solution, then by mixed solution, NaOH solution,
Ammonia spirit is mixed, and sediment is obtained after reacting, and sediment is filtered, is dry, then in the case where being sintered atmosphere,
Ternary precursor is sintered, nickel cobalt manganese hydroxide, i.e. ternary precursor are obtained；
S2, by lithium source, sintered ternary precursor mixing and ball milling, obtain mixed powder, then carry out mixed powder
Nickel-cobalt-manganese ternary material is obtained after sintering；
S3, nickel-cobalt-manganese ternary material, lithium chromate are mixed, then calcine, obtains the nickel cobalt manganese three of cladding lithium chromate
First material is to get to anode material for lithium-ion batteries.
A kind of lithium ion battery, including shell, the anode being placed in shell, cathode, diaphragm and electrolyte, diaphragm are located at institute
It states between anode and cathode, the anode includes above-mentioned anode material for lithium-ion batteries.
Embodiment 2
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, coprecipitation prepare spherical ternary precursor Ni0.6Co0.2Mn0.2(OH)2：By 6：2：2 molar ratios take LITHIUM BATTERY
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 3L of 1.0mol/L is made, is added according to the dosage of 8g/L anti-bad
Hematic acid 24g, obtains mixed solution；By the way of peristaltic pump cocurrent, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L
NaOH solution be placed in reaction kettle be mixed react, control ph 10.4, reaction temperature be 60 DEG C, mixing speed
For 500r/min, precipitation that reaction is generated is filtered 10 times by wind turbine or more, then dries 10h with blast drier, after put
Entering and is sintered 6h in oxygen atmosphere, sintering temperature is 600 DEG C, and oxygen flow 0.5L/min/kg obtains nickel cobalt manganese hydroxide,
That is ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material：By the above-mentioned ternary precursors prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
It is placed in ball milling in ball grinder, obtains mixed powder, the molar ratio of wherein ternary precursor and LITHIUM BATTERY lithium hydroxide is 1：1.05；
Mixed powder is placed in alumina crucible, is then sintered 6h at 500 DEG C, continues to increase temperature to being sintered 10h at 850 DEG C,
Obtain nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material lithium chromate cladding：It is 1 by molar ratio：0.02 nickel-cobalt-manganese ternary material and chromium
Sour lithium takes out calcining after being put into high-speed mixer and mixing stirring 1h, and calcination temperature obtains cladding chromium at 550 DEG C, calcination time 6h
The nickel-cobalt-manganese ternary material of sour lithium, i.e. anode material for lithium-ion batteries.
Embodiment 3
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, coprecipitation prepare spherical ternary precursor Ni0.6Co0.2Mn0.2(OH)2：By 6：2：2 molar ratios take LITHIUM BATTERY
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 3L of 1.0mol/L is made, is added according to the dosage of 8g/L anti-bad
Hematic acid 24g, obtains mixed solution；By the way of peristaltic pump cocurrent, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L
NaOH solution be placed in be mixed in reaction kettle and react, control ph 12, reaction temperature is 40 DEG C, and mixing speed is
500r/min, the precipitation that reaction is generated are filtered for 10 times or more by wind turbine, then dry 10h with blast drier, after be put into
8h is sintered in oxygen atmosphere, sintering temperature is 450 DEG C, and oxygen flow 1.5L/min/kg obtains nickel cobalt manganese hydroxide, i.e.,
Ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material：By the above-mentioned ternary precursors prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
Be placed in ball milling in ball grinder, obtain mixed powder, wherein ternary precursor, LITHIUM BATTERY lithium hydroxide molar ratio be 1：1.07；
Mixed powder is placed in alumina crucible, is then sintered 10h at 450 DEG C, continues to increase temperature to being sintered 20h at 650 DEG C,
Obtain nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material lithium chromate cladding：It is 1 by molar ratio：0.04 nickel-cobalt-manganese ternary material and chromium
Sour lithium takes out calcining after being put into high-speed mixer and mixing stirring 0.5h, calcines at 700 DEG C, calcination time 2h, obtains cladding chromic acid
The nickel-cobalt-manganese ternary material of lithium, i.e. anode material for lithium-ion batteries.
Embodiment 4
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, coprecipitation prepare spherical ternary precursor Ni0.6Co0.2Mn0.2(OH)2：By 6：2：2 molar ratios take LITHIUM BATTERY
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 3L of 1.0mol/L is made, is added according to the dosage of 8g/L anti-bad
Hematic acid 24g, obtains mixed solution；By the way of peristaltic pump cocurrent, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L
NaOH solution be placed in be mixed in reaction kettle and react, control ph 10, reaction temperature is 70 DEG C, and mixing speed is
500r/min, the precipitation that reaction is generated are filtered for 10 times or more by wind turbine, then dry 10h with blast drier, after be put into
4h is sintered in oxygen atmosphere, sintering temperature is 700 DEG C, and oxygen flow 0.lL/min/kg obtains nickel cobalt manganese hydroxide, i.e.,
Ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material：By the above-mentioned ternary precursors prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
Be placed in ball milling in ball grinder, obtain mixed powder, wherein ternary precursor, LITHIUM BATTERY lithium hydroxide molar ratio be 1：1；It will mix
It closes powder to be placed in alumina crucible, is then sintered 3h at 700 DEG C, continue to increase temperature to 8h is sintered at 1000 DEG C, obtain
Nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material lithium chromate cladding：It is 1 by molar ratio：0.06 nickel-cobalt-manganese ternary material and chromium
Sour lithium takes out calcining after being put into high-speed mixer and mixing stirring 2h, and calcination temperature obtains cladding chromium at 450 DEG C, calcination time 10h
The nickel-cobalt-manganese ternary material of sour lithium, i.e. anode material for lithium-ion batteries.
Embodiment 5
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, coprecipitation prepare spherical ternary precursor Ni0.6Co0.2Mn0.2(OH)2：By 6：2：2 molar ratios take LITHIUM BATTERY
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 3L of 1.0mol/L is made, is added according to the dosage of 8g/L anti-bad
Hematic acid 24g, obtains mixed solution；By the way of peristaltic pump cocurrent, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L
NaOH solution be placed in reaction kettle be mixed react, control ph 11.6, reaction temperature be 50 DEG C, mixing speed
For 500r/min, precipitation that reaction is generated is filtered 10 times by wind turbine or more, then dries 10h with blast drier, after put
Entering and is sintered 5h in oxygen atmosphere, sintering temperature is 500 DEG C, and oxygen flow 1.0L/min/kg obtains nickel cobalt manganese hydroxide,
That is ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material：By the above-mentioned ternary precursors prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
Be placed in ball milling in ball grinder, obtain mixed powder, wherein ternary precursor, LITHIUM BATTERY lithium hydroxide molar ratio be 1：1.03；
Mixed powder is placed in alumina crucible, is then sintered 9h at 500 DEG C, continues to increase temperature to being sintered 15h at 700 DEG C,
Obtain nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material lithium chromate cladding：It is 1 by molar ratio：0.08 nickel-cobalt-manganese ternary material and chromium
Sour lithium takes out calcining after being put into high-speed mixer and mixing stirring 1.5h, and calcination temperature is coated in 650 DEG C, calcination time 4h
The nickel-cobalt-manganese ternary material of lithium chromate, i.e. anode material for lithium-ion batteries.
Comparative example 1
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps：
S1, coprecipitation prepare spherical ternary precursor Ni0.6Co0.2Mn0.2(OH)2：By 6：2：2 molar ratios take LITHIUM BATTERY
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 3L of 1.0mol/L is made, is added according to the dosage of 8g/L anti-bad
Hematic acid 24g, obtains mixed solution；By the way of peristaltic pump cocurrent, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L
NaOH solution be placed in reaction kettle be mixed react, control ph 10.4, reaction temperature be 60 DEG C, mixing speed
For 500r/min, precipitation that reaction is generated is filtered 10 times by wind turbine or more, then dries 10h with blast drier, after put
Entering and is sintered 6h in oxygen atmosphere, sintering temperature is 600 DEG C, and oxygen flow 0.5L/min/kg obtains nickel cobalt manganese hydroxide,
That is ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material：By the above-mentioned ternary precursors prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
It is placed in ball milling in ball grinder, obtains mixed powder, the molar ratio of wherein ternary precursor and LITHIUM BATTERY lithium hydroxide is 1：1.05；
Mixed powder is placed in alumina crucible, is then sintered 6h at 500 DEG C, continues to increase temperature to being sintered 10h at 850 DEG C,
Obtain nickel-cobalt-manganese ternary material, i.e. anode material for lithium-ion batteries.
Test example 1
1.1 battery charging and discharging specific capacities are tested：The lithium ion cell positive material for respectively obtaining embodiment 2-5, comparative example 1
Positive plate is made in material, then assembles them into " 2032 " type button cell with routine techniques, in 2.75-4.3V voltage ranges, no
With charge-discharge test is carried out under current density, the charging and discharging capacity of different materials is recorded, as a result with reference to table 1.Wherein, rear 1C is followed
Ring 50 times, the discharge capacity * 100% of discharge capacity/the first week of cycle efficieny=50th week of battery.
1 embodiment 2-5 of table buckles electric performance test result with comparative example 1
1.2 25 DEG C of battery charge and discharge cycles are tested：Lithium ion battery to being obtained using embodiment 2-5, comparative example 1 respectively
Flexible package full battery made of positive electrode carries out cycle performance test, and test process is：Under the conditions of 25 DEG C, filled with 1C constant currents
Electricity is to 4.3V, after constant pressure to current reduction is 0.05C, after standing 30min, with 1C constant-current discharges to 3.0V, stands 30min, so
Afterwards to carry out charge-discharge test under different current densities, as a result with reference to table 2.Wherein, 1C is recycled 100 times, the cycle efficieny of battery
The discharge capacity * 100% of=the 100 week discharge capacity/the first week.
The full battery the performance test results of 2 embodiment 2-5 of table, comparative example 1
It can be seen that from table 1, table 2：It is bright that the present invention coats battery capacity made from the nickel-cobalt-manganese ternary material of lithium chromate
It is aobvious higher than uncoated, when the molar ratio of covering material lithium chromate and nickel-cobalt-manganese ternary material is 0.04：When 1, battery capacity is high
Up to 178.57mAh/g, and the first discharge specific capacity of battery made from uncoated ternary material is 175.42mAh/g, this is
Because lithium chromate coating layer material sheet has no effect on the insertion and abjection of lithium ion, the presence pair of clad as layer structure
The polarization of material has no influence in cyclic process for the first time；After 50 weeks cycles, circulating battery made from uncoated ternary material
Performance is worst.The molar ratio of covering material lithium chromate and nickel-cobalt-manganese ternary material is 0.04：When 1, the high rate performance of material is best,
2C and 5C discharge capacities are apparently higher than uncoated.But with the unobvious that the increase of covering amount, high rate performance improve, especially
When the molar ratio of covering material lithium chromate and nickel-cobalt-manganese ternary material is 0.08：It is forthright again compared to uncoated lithium chromate when 1
It can decline instead, be deteriorated.This is because the Li-Co-O solid solution shells containing Li ions are formed by being coated on particle surface,
Avoid being in direct contact for positive active material and electrolyte, it is suppressed that erosion of the electrolyte to positive electrode, to improve
The chemical property of material, but when clad is blocked up, the obstacle of ten diffusive migrations is increased, lead to the impedance of material after cladding
Increase, so that high rate performance decline is apparent.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of anode material for lithium-ion batteries, which is characterized in that the anode material for lithium-ion batteries includes containing nickel ternary
The interior nuclear phase layer of cobalt and manganese oxide and the surface coating layer containing lithium chromate.
2. anode material for lithium-ion batteries according to claim 1, which is characterized in that the anode material for lithium-ion batteries
Chemical formula is LixNiaCobMncCrdO2, wherein 1≤x≤l.07,0<a<L, 0<b<1,0<c<1,0.01≤d≤0.10, and a+b
+ c+d=1；Preferably, in chemical formula, 0.02≤d≤0.04；Preferably, the thickness of the surface coating layer containing lithium chromate
For 10-100nm.
3. a kind of preparation method of anode material for lithium-ion batteries according to claim 1 or claim 2, which is characterized in that including such as
Lower step：
S1, the sulfide solution of nickel, cobalt, manganese is hybridly prepared into mixed solution, then by mixed solution, NaOH solution, ammonium hydroxide
Solution is mixed, and sediment is obtained after reacting, and sediment is filtered, is dry, then in the case where being sintered atmosphere, by three
First presoma is sintered, and obtains nickel cobalt manganese hydroxide, i.e. ternary precursor；
S2, by lithium source, sintered ternary precursor mixing and ball milling, obtain mixed powder, be then sintered mixed powder
After obtain nickel-cobalt-manganese ternary material；
S3, nickel-cobalt-manganese ternary material, lithium chromate are mixed, then calcine, obtains the nickel-cobalt-manganese ternary material of cladding lithium chromate
Material is to get to anode material for lithium-ion batteries.
4. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S1, be mixed
Control ph is 10.0-12.0 in the process；Preferably, in S1, control ph is 10.4-11.6 in mixing process；It is preferred that
Ground, in S1, reaction temperature is 40-70 DEG C.
5. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S1, the sintering
Gas is selected from least one of oxygen, air, compressed air；Preferably, in S1, the flow for being sintered gas is 0.l-1.5L/
min/kg；Preferably, in S1, the temperature of sintering is 450-700 DEG C, time 4-8h；Preferably, in S1, the temperature of sintering is
600 DEG C, time 6h.
6. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S2, lithium source is selected from
At least one of the oxide of lithium, halide, hydroxide, carbonate, nitrate, acetate, oxalates；Preferably, S2
In, the molar ratio of ternary precursor and lithium source (in terms of elemental lithium) is 1：1-1.07.
7. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S2, the sintering
It is sintered 8-20h in the case where being sintered atmosphere, to be first sintered to rise at 650-1000 DEG C after 3-10h at 450-700 DEG C；It is preferred that
Ground, it is described to be sintered in the case where being sintered atmosphere in S2, it is first sintered after 6h to rise at 850 DEG C at 500 DEG C and is sintered 10h；It is preferred that
Ground, the sintering gas are selected from least one of oxygen, air, compressed air；Preferably, the gas stream of the sintering gas
Amount is 0.l-1.5L/min/kg.
8. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S3, the chromic acid
Lithium is selected from Li2CrO4·2H2O、Li2CrO4At least one of；Preferably, in S3, the nickel-cobalt-manganese ternary material and lithium chromate
Molar ratio be 1：0.02-0.08；Preferably, in S3, the molar ratio of the nickel-cobalt-manganese ternary material and lithium chromate is 1：0.02-
0.04；Preferably, in S3, the time of the stirring is 0.5-2h.
9. the preparation method of anode material for lithium-ion batteries according to claim 3, which is characterized in that in S3, the calcining
Temperature be 450-700 DEG C, calcination time 2-10h；Preferably, in S3, the temperature of the calcining is 550 DEG C, calcination time
For 6h.
10. a kind of lithium ion battery, including shell, the anode being placed in shell, cathode, diaphragm and electrolyte, diaphragm is located at institute
It states between anode and cathode, which is characterized in that the active material of the anode is any one of the claim 1-9 lithium-ion electrics
Pond positive electrode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109585839A (en) * | 2019-01-16 | 2019-04-05 | 合肥国轩高科动力能源有限公司 | A kind of alumina-coated nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN111430700A (en) * | 2019-10-10 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery |
| CN114373918A (en) * | 2022-01-12 | 2022-04-19 | 河北科技大学 | Silicon-carbon negative electrode material and preparation method thereof |
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| CN105161710A (en) * | 2015-08-31 | 2015-12-16 | 宁波金和锂电材料有限公司 | Battery cathode material, preparation method thereof and lithium ion battery |
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| CN109585839A (en) * | 2019-01-16 | 2019-04-05 | 合肥国轩高科动力能源有限公司 | A kind of alumina-coated nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN111430700A (en) * | 2019-10-10 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery |
| CN111430700B (en) * | 2019-10-10 | 2022-07-22 | 蜂巢能源科技有限公司 | Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery |
| CN114373918A (en) * | 2022-01-12 | 2022-04-19 | 河北科技大学 | Silicon-carbon negative electrode material and preparation method thereof |
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