CN110451585A - A kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery - Google Patents
A kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery Download PDFInfo
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Abstract
The present invention relates to a kind of nickelic, long circulating monocrystalline NCM anode material for lithium-ion batteries preparation methods, it is the following steps are included: (1) mixes soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide with ammonium hydroxide, and progress constant temperature co-precipitation in reaction kettle is flowed into, obtain nickelic NCM ternary precursor material；(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are uniformly mixed, dried；It is carried out under oxygen-enriched atmosphere once sintered, obtains spherical nickelic NCM tertiary cathode material；(3) it is crushed, crushes, sieving, obtaining nickelic NCM tertiary cathode material；(4) by above-mentioned nickelic NCM tertiary cathode material and covering B, wet-mixing drying is carried out；In oxygen-enriched atmosphere double sintering, it is crushed, crushes, sieving, obtaining high Ni-monocrystal NCM anode material for lithium-ion batteries.Positive electrode prepared by the present invention, has many advantages, such as high capacity, good cycle, and compacted density is high.
Description
Technical field
The present invention relates to new-energy automobile lithium ion power battery technology fields, and in particular to a kind of high Ni-monocrystal lithium from
The preparation method of sub- cell positive material.
Background technique
Lithium-ion-power cell is that new-energy automobile develops core technology link, and wherein the superiority and inferiority of positive electrode is even more to restrict
The most important thing of power battery development.With the increase of electric car course continuation mileage and gradually decreasing for public subsidies, to dynamic
The energy density of power battery requires also higher and higher.
Nowadays, high gram volume, high voltage, long circulating, inexpensive positive electrode are the demands in power battery market.Positive material
Material also develops from initial NCM111 to NCM523, NCM622 and NCM811, the direction NCA.Nickel in positive electrode is improved to contain
Amount, while cobalt content is reduced, the cost of raw material can be reduced simultaneously improving material gram volume, therefore, high-nickel material is to be promoted
The key of positive added value of product, and the highland of major competition among enterprises both at home and abroad.
But there are problems for the nickelic positive electrode of conventional second particle, such as: (1) since second particle is to reunite
The form of body exists, and bulk density is lower, causes compacted density lower；(2) under higher compacting, secondary spherical particle can be broken
It is broken, increase the specific surface area of material, side reaction aggravation causes chemical property to decline；(3) in high voltage charge and discharge process
In, secondary spherical granular materials crystal structure is easy to collapse, and is easy to produce gas etc..However, the positive electrode of monocrystalline pattern, not only
The high temperature circulation of polycrystalline material can be effectively improved, produce the problems such as gas, and be also equipped with plurality of advantages, such as: (1) mono-crystalline structures machine
Tool intensity is high, and compacted density is big, is not easy to crush；(2) monocrystal material surface residual alkali is low, reduces the side reaction of material and electrolyte；
(3) the advantages that single-crystal surface is smooth, and particle is uniform, comes into full contact with conductive agent, is conducive to the transmission of lithium ion.In addition, in height
Under the application conditions of voltage 4.3V, 4.4V, capacity, circulation advantage, performance it is more obvious.
Currently, " nickelic NCM second particle positive electrode " that there are room temperature and high temperature cyclic performance is poor, high rate performance is poor, pressure
The problems such as real density is low and storage capacity is poor.The present invention is directed to this problem, probe into it is a kind of can large-scale application method, preparation
With high voltage, high-pressure solid, macrocyclic high Ni-monocrystal NCM tertiary cathode material.
Summary of the invention
Based on the above prior art, the purpose of the present invention is to provide a kind of high Ni-monocrystal anode material for lithium-ion batteries
Preparation method, high Ni-monocrystal anode material for lithium-ion batteries produced by the present invention have high capacity, good cycle, compacted density
The advantages that high.
In order to achieve the goal above, the technical solution adopted by the present invention are as follows: a kind of nickelic, long circulating monocrystalline lithium ion battery
Method for preparing anode material, comprising the following steps:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent enter with bottom liquid and
Constant temperature co-precipitation is carried out in the reaction kettle of protective gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is done
It is dry to obtain spherical nickelic NCM ternary precursor material；
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are mixed equal
It is even；Then, slurry is dried in such a way that dynamic rotary is dry；Under oxygen-enriched atmospheric condition, by the powder after drying
End carries out once sintered；
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains disperse point
The nickelic NCM tertiary cathode material of cloth, amorphous state；
(4) above-mentioned nickelic NCM tertiary cathode material and covering B under vacuum conditions, are adopted after carrying out wet-mixing
Slurry is dried with dynamic rotary dry mode, drying terminates to carry out double sintering under oxygen-enriched atmospheric condition, break
Broken, crushing, sieving, obtain high Ni-monocrystal NCM anode material for lithium-ion batteries.
In order to preferably realize the present invention, further, coprecipitation reaction condition in the step (1) is as follows: in solvent
Soluble nickel ion: cobalt ions: molar ratio=x:y:z of manganese ion；Wherein x+y+z=1,0.6 < x < 1,0 < y < 0.5,0 < z <
0.5；
In the mixed solvent nickel ion, cobalt ions, manganese ion total concentration be 0.5~2.0mol/L,
Atmosphere: nitrogen or inert gas,
Mixing speed: 500~2000r/min；Reaction temperature: 30~80 DEG C,
Alkali metal hydroxide: NaOH；PH value: 10~12,
Ammonia concn: 0.1~0.6mol/L,
Digestion time: 10~48h,
Obtain spherical nickelic ternary precursor NixCoyMnz (OH)2Average grain diameter D50:3~5 μm；Specific surface area BET:
>20m2/g；Apparent density: > 1.0g/cm2, tap density: > 1.5g/cm2。
In order to preferably realize the present invention, further, in the step (2),
Ingredient Li/Me 1. (Ni+Co+Mn) molar ratio: 1.02~1.1；
2. the total metallic element weight of metal element A accounting presoma in oxide addition: 0.1~1wt%；
Oxide addition is optional: Al2O3、ZrO、MgO、CaO、TiO2、SiO2、V2O5、Sc2O3、Nb2O5、Ta2O5、Y2O3In
One or more；
3. the liquid medium of material by wet type mixing is water, alcohol, acetone, N-Methyl pyrrolidone, polyethylene glycol, isopropanol, third
The one or more of acrylamide；
Wherein solid-liquid mass ratio: 1~5；
In order to preferably realize the present invention, further, in the step (2), mixing equipment can be selected high speed ball mill,
One of high-speed mixer, coulter type mixer, 2~8h of mixing time, 30~150Hz of mixing frequency；Dynamic drying equipment
Using colter vacuum drier or double-cone vacuum dryer, drying temperature is 100~150 DEG C, drying time: 8~for 24 hours；Sintering
Reaction condition be oxygen atmosphere volumetric concentration 30~99%, 300~800 DEG C of sintering temperature, 3~10 DEG C/min of heating rate,
Soaking time 6~for 24 hours.
In order to preferably realize the present invention, further, in the step (2), it is once sintered after nickelic tertiary cathode
Material is part aggregate, average grain diameter D50:3~7 μm；Specific surface area BET:0.5 < y < 1m2/g.
In order to preferably realize the present invention, it is nickelic further, in the step (3) to obtain Dispersed precipitate, amorphous state
The condition of NCM tertiary cathode material is that jaw is broken, to roller crack spacing: 0.1~0.5mm；Admission pressure: 0.2~5MPa；Air-flow
Crush frequency: 20~50Hz；Grade frequency: 20~200Hz.The nickelic NCM ternary of Dispersed precipitate, amorphous state is obtained after crushing just
Pole material, average grain diameter D50:1~5 μm, specific surface area BET:0 < y < 5m2/g。
In order to preferably realize the present invention, further, in the step (4): covering B uses collosol and gel legal system
Standby, step is to select metallic element for one or more of aluminium, zirconium, magnesium, calcium, titanium, silicon, vanadium, scandium, niobium, tantalum, yttrium etc., is contained
One or more of the optional sulfate of B compound, nitrate, phosphate or chlorate, metallorganic, collosol and gel preparation
The concentration of boride alloy in the process are as follows: 0.02~1.0mol/L, reaction temperature: 25~65 DEG C, the reaction time: 2~12h, pH model
It encloses: 8~11, element B accounts for an imitation frosted glass weight: 0.1~1.0wt% in covering.
In order to preferably realize the present invention, further, mixing equipment selects high speed ball mill, height in the step (4)
One of fast mixing machine, coulter type mixer, 2~8h of mixing time, 30~150HZ of mixing frequency；The choosing of dynamic drying equipment
With colter vacuum drier or double-cone vacuum dryer, 100~150 DEG C of drying temperature, drying time 8~for 24 hours；Double sintering is anti-
Answer condition as follows, the volumetric concentration 30~99% of oxygen atmosphere, 300~800 DEG C of sintering temperature, 3~10 DEG C/min of heating rate,
Soaking time 6~for 24 hours.
In order to preferably realize the present invention, further, high Ni-monocrystal positive electrode, chemistry are obtained in the step (4)
Formula LiNixCoyMnzO2, in which: table is compared in x+y+z=1,0.6 < x < 1,0 < y < 0.5,0 < z < 0.5, average grain diameter D50:1~5 μm
Area B ET:0 < y < 2m2/g。
In order to preferably realize the present invention, further, the positive electrode obtained in the step (4) is assembled into button electricity
Pond, method particularly includes: positive electrode, acetylene black, Kynoar PVDF are weighed according to the mass ratio of 95:2.5:2.5, are mixed
Close uniformly, be added NMP stir 4h, slurry is made, is then coated uniformly on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, cut
For the positive plate of diameter 14mm；Using the lithium piece of diameter 16mm as negative electrode tab, 5 drop 1mol/L LiPFO4+1mol/L are added dropwise in syringe
DEC/EC isometric mixed solution is electrolyte, and microporous polypropylene membrane is diaphragm, is detained in the glove box full of argon gas
The assembling of formula battery.
Beneficial effect
Beneficial effects of the present invention are as follows:
(1) present invention preparation has high voltage, high-pressure solid, macrocyclic high Ni-monocrystal NCM tertiary cathode material.Its technique
Process: Co deposited synthesis ternary NCM presoma is used first, ingredient is then carried out by the way of wet process high speed mixing, is mentioned
The consistency of high material then carries out once sintered；Mechanical treatment, sol-gal process realize the works such as in-stiu coating, double sintering
Skill obtains high voltage, high-pressure solid, the high nickel-cobalt lithium manganate cathode material of macrocyclic monocrystalline.Wherein, wet process in-stiu coating has one
Cause property is good, realizes the purpose that nanoscale uniformly coats, and then improve the uniformity and stability of material.
(2) wet process high speed mixing matches lithium, and molecular level may be implemented and uniformly mix, and overcomes that dry mixing is non-uniform to ask
Topic is conducive to the suction lithium reaction of subsequent high temperature sintering, improves reactivity.
(3) sol-gal process synthesizes covering, realizes all standing of basis material, reaches the uniform cladding of molecular level,
Structural stability of the material in electrochemistry cyclic process can be improved, and then improve the room temperature and high temperature cyclic performance of material.
(4) wet process matches lithium and wet process in-stiu coating, can reduce the Sintering Problem of a burning or two burnings, be conducive to monocrystal material
Aftertreatment technology.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Fig. 2 is the microstructure figure of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Fig. 3 is the particle size distribution figure of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Fig. 4 is the XRD diffraction spectrogram of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Fig. 5 is the gram volume of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Fig. 6 is the full electricity circulation figure of the high nickel-cobalt lithium manganate cathode material of monocrystalline of the present invention
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment 1
The present embodiment provides a kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, including following step
It is rapid:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent enter with bottom liquid and
Constant temperature co-precipitation is carried out in the reaction kettle of protective gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is done
It is dry to obtain spherical nickelic NCM ternary precursor material；Wherein coprecipitation reaction condition is as follows: according to nickel ion: cobalt ions: manganese
Ion molar ratio is the ratio of 0.85:0.1:0.05, and preparing metal ion concentration summation is 2mol/L；Prepare NaOH solution concentration
8mol/L prepares ammonia spirit concentration 120g/L；By three kinds of solution respectively with 80ml/min, 10ml/min and 10ml/min simultaneously
It is passed through in reaction kettle, control pH value is 11.5, and temperature is 55 DEG C, successive reaction 20h, passes through respectively and is aged, washs, drying, obtaining
The persursor material Ni for being 4 μm to D500.85Co0.1Mn0.05(OH)2。
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are mixed equal
It is even；Its method are as follows: ingredient Li/Me (Ni+Co+Mn) molar ratio: 1.06；The mass fraction of the total material of additional amount Zhan of zr element is
Mixed slurry is injected in colter vacuum drier, is stirred drying by 5000ppmw.Finally, in high purity oxygen gas condition
Under, progress is once sintered, and temperature is 850 DEG C, keeps the temperature 15h, and cooling, jaw is broken, to roller, crushing, sieving, and basis material is burnt in acquisition one
LiNi0.85Co0.1Mn0.05O2。
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains disperse point
The nickelic NCM tertiary cathode material of cloth, amorphous state, process conditions are that jaw is broken, to roller crack spacing: 0.1mm；Air inlet pressure
Power: 0.2MPa；Air-flow crushing frequency: 20Hz；Grade frequency: 40Hz.The nickelic NCM of Dispersed precipitate, amorphous state is obtained after crushing
Tertiary cathode material, average grain diameter D50:1~5 μm；Specific surface area BET:0 < y < 5m2/g。
(4) above-mentioned nickelic NCM tertiary cathode material and covering B under vacuum conditions, are adopted after carrying out wet-mixing
Slurry is dried with dynamic rotary dry mode, drying terminates to carry out double sintering under oxygen-enriched atmospheric condition, break
Broken, crushing, sieving, obtain high Ni-monocrystal NCM anode material for lithium-ion batteries.Wherein covering B is prepared using sol-gal process,
Its step is that sulfuric acid aluminum nano-powder is added in lithium hydroxide solution, and pH control is carried out in 10.3~10.7, temperature 45 C
Water bath with thermostatic control heating stirring 8h, prepares the Aluminum sol of solid content 1wt%.The Aluminum sol of preparation is injected into one in the form of hydrojet
It burns in basis material, is stirred, mixes, dries in plough coulter type vacuum drier；Then by the material after drying oxygen-enriched
Atmospheric condition under, carry out double sintering, the volumetric concentration 45% of oxygen atmosphere, 4 DEG C/min of heating rate, controlled at
650 DEG C, 10h is kept the temperature, cooling, jaw is broken, to roller, crushing, sieving, obtains the nickelic positive electrode of monocrystalline type
LiNi0.85Co0.1Mn0.05O2。
The positive electrode of acquisition is assembled into button cell, method particularly includes: positive electrode, acetylene black, Kynoar
PVDF is weighed according to the mass ratio of 95:2.5:2.5, is uniformly mixed, NMP stirring 4h is added, and slurry is made, then uniformly applies
It overlays on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm；Using the lithium piece of diameter 16mm as
Negative electrode tab, it is electrolyte, polypropylene that the isometric mixed solution of 5 drop 1mol/L LiPFO4+1mol/L DEC/EC, which is added dropwise, in syringe
Microporous barrier is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
The positive electrode of acquisition is subjected to battery assembly and button electrical testing, by testing, the use compacted density of the material:
3.52g/cm3；Under the conditions of 3.0~4.3V, 0.1C, discharge capacity for the first time: 214mAh/g；Under the conditions of 3.0~4.3V, 1C/1C, 50
All capacity retention ratios are as follows: 98.1%.
Embodiment 2
The present embodiment provides a kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, including following step
It is rapid:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent enter with bottom liquid and
Constant temperature co-precipitation is carried out in the reaction kettle of protective gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is done
It is dry to obtain spherical nickelic NCM ternary precursor material；Wherein coprecipitation reaction condition is as follows: according to nickel ion: cobalt ions: manganese
Ion molar ratio is the solution of 0.8:0.1:0.1, and preparing metal ion concentration summation is 1.5mol/L, prepares NaOH solution concentration
8mol/L prepares ammonia spirit concentration: 100g/L；Three kinds of solution are same with 80ml/min, 10ml/min and 10ml/min respectively
When be passed through in reaction kettle, control pH value be 11.3, temperature be 55 DEG C, successive reaction 20h, respectively by ageing, washing, drying,
Obtain the persursor material Ni that D50 is 3 μm0.8Co0.1Mn0.1(OH)2。
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are mixed equal
It is even；Its method are as follows: ingredient Li/Me (Ni+Co+Mn) molar ratio: 1.05；The mass fraction of the total material of additional amount Zhan of element silicon is
Mixed slurry is injected in colter vacuum drier, is stirred drying by 3000ppmw.Finally, in high purity oxygen gas condition
Under, progress is once sintered, and temperature is 870 DEG C, keeps the temperature 15h, and cooling, jaw is broken, to roller, crushing, sieving, and basis material is burnt in acquisition one
LiNi0.8Co0.1Mn0.1O2。
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains disperse point
The nickelic NCM tertiary cathode material of cloth, amorphous state, process conditions are that jaw is broken, to roller crack spacing: 0.2mm；Air inlet pressure
Power: 1MPa；Air-flow crushing frequency: 30Hz；Grade frequency: 100Hz.The nickelic NCM tri- of Dispersed precipitate, amorphous state is obtained after crushing
First positive electrode, average grain diameter D50:1~5 μm；Specific surface area BET:0 < y < 5m2/g。
(4) above-mentioned nickelic NCM tertiary cathode material and covering B under vacuum conditions, are adopted after carrying out wet-mixing
Slurry is dried with dynamic rotary dry mode, drying terminates to carry out double sintering under oxygen-enriched atmospheric condition, break
Broken, crushing, sieving, obtain high Ni-monocrystal NCM anode material for lithium-ion batteries.Wherein covering B is prepared using sol-gal process,
Its step is, boehmite nanometer powder is added in lithium hydroxide solution, and pH control is 10.8~11.2, temperature 60 C, into
Row water bath with thermostatic control heating stirring 8h, prepares the Aluminum sol of solid content 1wt%.The Aluminum sol of preparation is injected into the form of hydrojet
One burns in basis material, is stirred, mixes, dries in plough coulter type vacuum drier；Then by the material after drying in richness
Under the atmospheric condition of oxygen, double sintering, the volumetric concentration 55% of oxygen atmosphere, 5 DEG C/min of heating rate, temperature 700 are carried out
DEG C, 10h is kept the temperature, cooling, jaw is broken, to roller, crushing, sieving, obtains the nickelic positive electrode LiNi of monocrystalline type0.8Co0.1Mn0.1O2。
The positive electrode of acquisition is assembled into button cell, method particularly includes: positive electrode, acetylene black, Kynoar
PVDF is weighed according to the mass ratio of 95:2.5:2.5, is uniformly mixed, NMP stirring 4h is added, and slurry is made, then uniformly applies
It overlays on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm；Using the lithium piece of diameter 16mm as
Negative electrode tab, it is electrolyte, polypropylene that the isometric mixed solution of 5 drop 1mol/L LiPFO4+1mol/L DEC/EC, which is added dropwise, in syringe
Microporous barrier is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
The positive electrode of acquisition is subjected to battery assembly and button electrical testing, by testing, the use compacted density of the material:
3.55g/cm3；Under the conditions of 3.0-4.3V, 0.1C, discharge capacity for the first time: 204mAh/g；Under the conditions of 3.0-4.3V, 1C/1C, 50
All capacity retention ratios are as follows: 98.4%.
Embodiment 3
The present embodiment provides a kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, including following step
It is rapid:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent enter with bottom liquid and
Constant temperature co-precipitation is carried out in the reaction kettle of protective gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is done
It is dry to obtain spherical nickelic NCM ternary precursor material；Wherein coprecipitation reaction condition is as follows: according to nickel ion: cobalt ions: manganese
Ion molar ratio is the solution of 0.7:0.15:0.15, and preparing metal ion concentration summation is 1.5mol/L, and it is dense to prepare NaOH solution
8mol/L is spent, ammonia spirit concentration 100g/L is prepared；Three kinds of solution are same with 70ml/min, 15ml/min and 15ml/min respectively
When be passed through in reaction kettle, control pH value be 11.2, temperature be 50 DEG C, successive reaction for 24 hours, respectively by ageing, washing, drying,
Obtain the persursor material Ni that D50 is 4 μm0.7Co0.15Mn0.15(OH)2。
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are mixed equal
It is even；Its method are as follows: ingredient Li/Me (Ni+Co+Mn) molar ratio: 1.04；The mass fraction of the total material of additional amount Zhan of magnesium elements is
Mixed slurry is injected in colter vacuum drier, is stirred drying by 2000ppmw.Finally, in high purity oxygen gas condition
Under, progress is once sintered, and temperature is 890 DEG C, keeps the temperature 15h, and cooling, jaw is broken, to roller, crushing, sieving, and basis material is burnt in acquisition one
LiNi0.7Co0.15Mn0.15O2。
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains disperse point
The nickelic NCM tertiary cathode material of cloth, amorphous state, process conditions are that jaw is broken, to roller crack spacing 0.4mm, admission pressure
3MPa, air-flow crushing frequency 40Hz, grade frequency 150Hz are obtaining the nickelic NCM ternary of Dispersed precipitate, amorphous state just after crushing
Pole material, average grain diameter D50:1~5 μm；Specific surface area BET:0 < y < 5m2/g。
(4) above-mentioned nickelic NCM tertiary cathode material and covering B under vacuum conditions, are adopted after carrying out wet-mixing
Slurry is dried with dynamic rotary dry mode, drying terminates to carry out double sintering under oxygen-enriched atmospheric condition, break
Broken, crushing, sieving, obtain high Ni-monocrystal NCM anode material for lithium-ion batteries.Wherein covering B is prepared using sol-gal process,
Its step is to dilute butyl titanate solvent, while being added in alcohol solvent, glacial acetic acid is added dropwise, pH control is 2.0~4.0, temperature
45 DEG C of degree carries out water bath with thermostatic control heating stirring 1h, prepares the titanium colloidal sol of solid content 1wt%.By the titanium colloidal sol of preparation with hydrojet
Form is injected into a burning basis material, is stirred, mixes, is dried in plough coulter type vacuum drier；Then after drying
Material under oxygen-enriched atmospheric condition, carry out double sintering, the volumetric concentration 75% of oxygen atmosphere, 7 DEG C/min of heating rate,
Temperature is 750 DEG C, keeps the temperature 10h, and cooling, jaw is broken, to roller, crushing, sieving, obtains the nickelic positive electrode of monocrystalline type
LiNi0.7Co0.15Mn0.15O2。
The positive electrode of acquisition is assembled into button cell, method particularly includes: positive electrode, acetylene black, Kynoar
PVDF is weighed according to the mass ratio of 95:2.5:2.5, is uniformly mixed, NMP stirring 4h is added, and slurry is made, then uniformly applies
It overlays on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm；Using the lithium piece of diameter 16mm as
Negative electrode tab, it is electrolyte, polypropylene that the isometric mixed solution of 5 drop 1mol/L LiPFO4+1mol/L DEC/EC, which is added dropwise, in syringe
Microporous barrier is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
The positive electrode of acquisition is subjected to battery assembly and button electrical testing, by testing, the use compacted density of the material:
3.6g/cm3；Under the conditions of 3.0-4.3V, 0.1C, discharge capacity for the first time: 197mAh/g；Under the conditions of 3.0-4.3V, 1C/1C, 50
All capacity retention ratios are as follows: 98.7%.
Embodiment 4
The present embodiment provides a kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, including following step
It is rapid:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent enter with bottom liquid and
Constant temperature co-precipitation is carried out in the reaction kettle of protective gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is done
It is dry to obtain spherical nickelic NCM ternary precursor material；Wherein coprecipitation reaction condition is as follows: according to nickel ion: cobalt ions: manganese
Ion molar ratio is the solution of 0.6:0.2:0.2, and preparing metal ion concentration summation is 2.0mol/L, and it is dense to prepare NaOH solution:
8.5mol/L prepares ammonia spirit concentration 100g/L；Three kinds of solution are same with 60ml/min, 15ml/min and 15ml/min respectively
When be passed through in reaction kettle, control pH value be 10.8, temperature be 50 DEG C, successive reaction for 24 hours, respectively by ageing, washing, drying,
Obtain the persursor material Ni that D50 is 3.5um0.6Co0.2Mn0.2(OH)2。
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are mixed equal
It is even；Its method are as follows: ingredient Li/Me (Ni+Co+Mn) molar ratio: 1.03, the mass fraction of the total material of additional amount Zhan of yttrium is
Mixed slurry is injected in colter vacuum drier, is stirred drying by 1500ppmw.Finally, in high purity oxygen gas condition
Under, progress is once sintered, and temperature is 940 DEG C, keeps the temperature 15h, and cooling, jaw is broken, to roller, crushing, sieving, and basis material is burnt in acquisition one
LiNi0.6Co0.2Mn0.2O2。
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains disperse point
The nickelic NCM tertiary cathode material of cloth, amorphous state, process conditions are that jaw is broken, to roller crack spacing 0.5mm；Admission pressure
5MPa；Air-flow crushing frequency 50Hz；20~200Hz of grade frequency obtains the nickelic NCM tri- of Dispersed precipitate, amorphous state after crushing
First positive electrode, average grain diameter D50:1~5 μm；Specific surface area BET:0 < y < 5m2/g。
(4) above-mentioned nickelic NCM tertiary cathode material and covering B under vacuum conditions, are adopted after carrying out wet-mixing
Slurry is dried with dynamic rotary dry mode, drying terminates to carry out double sintering under oxygen-enriched atmospheric condition, break
Broken, crushing, sieving, obtain high Ni-monocrystal NCM anode material for lithium-ion batteries.Wherein covering B is prepared using sol-gal process,
Its step is, using ethyl orthosilicate as the presoma of colloidal sol, in addition water, alcohol solvent, N-N-dimethylformamide is addition
Lithium hydroxide solvent is added dropwise in agent, and pH control is 9.0~11.0, and temperature 50 C carries out water bath with thermostatic control heating stirring 4h, and preparation is solid
The silica solution of content 1wt%.The silica solution of preparation is injected into a burning basis material in the form of hydrojet, in plough coulter type vacuum
It is stirred, mixes, dries in drying machine；Then by the material after drying under oxygen-enriched atmospheric condition, double sintering is carried out,
The volumetric concentration 95% of oxygen atmosphere, 10 DEG C/min of heating rate, temperature are 800 DEG C, keep the temperature 10h, and cooling, jaw is broken, to roller, powder
Broken, sieving, obtains the nickelic positive electrode LiNi of monocrystalline type0.6Co0.2Mn0.2O2。
The positive electrode of acquisition is assembled into button cell, method particularly includes: positive electrode, acetylene black, Kynoar
PVDF is weighed according to the mass ratio of 95:2.5:2.5, is uniformly mixed, NMP stirring 4h is added, and slurry is made, then uniformly applies
It overlays on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm；Using the lithium piece of diameter 16mm as
Negative electrode tab, it is electrolyte, polypropylene that the isometric mixed solution of 5 drop 1mol/L LiPFO4+1mol/L DEC/EC, which is added dropwise, in syringe
Microporous barrier is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
The positive electrode of acquisition is subjected to battery assembly and button electrical testing, by testing, the use compacted density of the material:
3.66g/cm3；Under the conditions of 3.0-4.3V, 0.1C, discharge capacity for the first time: 190mAh/g；Under the conditions of 3.0-4.3V, 1C/1C, 50
All capacity retention ratios are as follows: 98.8%.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, which comprises the following steps:
(1) soluble nickel salt, cobalt salt, manganese salt, alkali metal hydroxide are mixed with ammonium hydroxide, cocurrent, which enters, has bottom liquid and protection
Constant temperature co-precipitation is carried out in the reaction kettle of gas, and sufficiently spilling material is separated by solid-liquid separation after reaction, be aged, be centrifuged, is dried
To spherical nickelic NCM ternary precursor material；
(2) by the way of wet process high speed mixing, nickelic NCM ternary precursor, lithium hydroxide, additive A are uniformly mixed；So
Afterwards, slurry is dried in such a way that dynamic rotary is dry；Under oxygen-enriched atmospheric condition, the powder after drying is carried out
It is once sintered；
(3) step (2) is obtained spherical nickelic NCM tertiary cathode material to be crushed, crush, be sieved, obtains Dispersed precipitate, nothing
The nickelic NCM tertiary cathode material for the state that shapes；
(4) by above-mentioned nickelic NCM tertiary cathode material and covering B, after carrying out wet-mixing, under vacuum conditions, using dynamic
The mode of state rotary drying dries slurry, and drying terminates to carry out double sintering, broken, powder under oxygen-enriched atmospheric condition
Broken, sieving, obtains high Ni-monocrystal NCM anode material for lithium-ion batteries.
2. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is that coprecipitation reaction condition in the step (1) is as follows: soluble nickel ion in solvent: cobalt ions: manganese ion rubs
You are ratio=x:y:z；Wherein x+y+z=1,0.6 < x < 1,0 < y < 0.5,0 < z < 0.5；
In the mixed solvent nickel ion, cobalt ions, manganese ion total concentration be 0.5~2.0mol/L,
Atmosphere: nitrogen or inert gas,
Mixing speed: 500~2000r/min；Reaction temperature: 30~80 DEG C,
Alkali metal hydroxide: NaOH；PH value: 10~12,
Ammonia concn: 0.1~0.6mol/L,
Digestion time: 10~48h,
Obtain spherical nickelic ternary precursor NixCoyMnz (OH)2Average grain diameter D50:3~5 μm；Specific surface area BET: >
20m2/g；Apparent density: > 1.0g/cm2, tap density: > 1.5g/cm2。
3. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is, in the step (2),
Ingredient Li/Me 1. (Ni+Co+Mn) molar ratio: 1.02~1.1；
2. the total metallic element weight of metal element A accounting presoma in oxide addition: 0.1~1wt%；
Oxide addition is optional: Al2O3、ZrO、MgO、CaO、TiO2、SiO2、V2O5、Sc2O3、Nb2O5、Ta2O5、Y2O3In one
Kind is several；
3. the liquid medium of material by wet type mixing is water, alcohol, acetone, N-Methyl pyrrolidone, polyethylene glycol, isopropanol, acryloyl
The one or more of amine；
Wherein solid-liquid mass ratio: 1~5.
4. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is, in the step (2), high speed ball mill, high-speed mixer, one in coulter type mixer is can be selected in mixing equipment
Kind, 2~8h of mixing time, 30~150Hz of mixing frequency；Dynamic drying equipment is dry using colter vacuum drier or bipyramid vacuum
Dry machine, drying temperature are 100~150 DEG C, drying time: 8~for 24 hours；Sintering reaction condition is the volumetric concentration 30 of oxygen atmosphere
~99%, 300~800 DEG C of sintering temperature, 3~10 DEG C/min of heating rate, soaking time 6~for 24 hours.
5. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is, in the step (2), it is once sintered after nickelic tertiary cathode material be part aggregate, average grain diameter D50:3~
7μm；Specific surface area BET:0.5 < y < 1m2/g.
6. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is, obtains Dispersed precipitate in the step (3), the condition of the nickelic NCM tertiary cathode material of amorphous state is, jaw is broken, right
Roller crack spacing: 0.1~0.5mm；Admission pressure: 0.2~5MPa；Air-flow crushing frequency: 20~50Hz；Grade frequency: 20~
200Hz.The nickelic NCM tertiary cathode material of Dispersed precipitate, amorphous state, average grain diameter D50:1~5 μm are obtained after crushing；Compare table
Area B ET:0 < y < 5m2/g。
7. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is that in the step (4): covering B is prepared using sol-gal process, step be select metallic element for aluminium, zirconium,
One or more of magnesium, calcium, titanium, silicon, vanadium, scandium, niobium, tantalum, yttrium etc., the optional sulfate of boride alloy, nitrate, phosphate
Or one or more of chlorate, metallorganic, the concentration of boride alloy in collosol and gel preparation process are as follows: 0.02~
1.0mol/L, reaction temperature: 25~65 DEG C, the reaction time: 2~12h, pH range: 8~11, element B accounts for an imitation frosted glass in covering
Weight: 0.1~1.0wt%.
8. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is that mixing equipment selects one of high speed ball mill, high-speed mixer, coulter type mixer in the step (4), mixes
Expect 2~8h of time, 30~150HZ of mixing frequency；Dynamic drying equipment selects colter vacuum drier or double-cone vacuum dryer,
100~150 DEG C of drying temperature, drying time 8~for 24 hours；Double sintering reaction condition is as follows, and the volumetric concentration 30 of oxygen atmosphere~
99%, 300~800 DEG C of sintering temperature, 3~10 DEG C/min of heating rate, soaking time 6~for 24 hours.
9. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery, special
Sign is, high Ni-monocrystal positive electrode, chemical formula LiNixCoyMnzO are obtained in the step (4)2, in which: x+y+z=1,
0.6 < x < 1,0 < y < 0.5,0 < z < 0.5, average grain diameter D50:1~5 μm, specific surface area BET:0 < y < 2m2/g。
10. one kind according to claim 1 is nickelic, long circulating monocrystalline method for preparing anode material of lithium-ion battery,
It being characterized in that, the positive electrode obtained in the step (4) is assembled into button cell, method particularly includes: positive electrode, acetylene
Black, Kynoar PVDF is weighed according to the mass ratio of 95:2.5:2.5, is uniformly mixed, NMP stirring 4h is added, and slurry is made
Material, is then coated uniformly on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm；With diameter
As negative electrode tab, syringe is added dropwise the isometric mixed solution of 5 drop 1mol/L LiPFO4+1mol/L DEC/EC and is the lithium piece of 16mm
Electrolyte, microporous polypropylene membrane are diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
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