CN105958063A - Preparation method of nickel-cobalt-aluminum cathode material used for lithium-ion battery - Google Patents
Preparation method of nickel-cobalt-aluminum cathode material used for lithium-ion battery Download PDFInfo
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- CN105958063A CN105958063A CN201610539571.1A CN201610539571A CN105958063A CN 105958063 A CN105958063 A CN 105958063A CN 201610539571 A CN201610539571 A CN 201610539571A CN 105958063 A CN105958063 A CN 105958063A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nickel-cobalt-aluminum cathode material used for a lithium-ion battery. The preparation method comprises a precursor preparation step and a mixed calcination step. According to the method, a precursor having quadrate secondary particles is firstly prepared by utilizing the role of a complexing agent, and then the precursor is mixed with an aluminum-containing compound and a lithium-containing compound for calcination so as to obtain a LiNi0.8Co0.15Al0.05O2 cathode material having the quadrate secondary particles. The secondary particles of the LiNi0.8Co0.15Al0.05O2 cathode material obtained through the preparation method are of a quadrate structure and excellent in electrochemical performance; the technology is simple and reliable; and the preparation method is suitable for large-scale and commercialized production of the LiNi0.8Co0.15Al0.05O2 cathode material having the quadrate secondary particles.
Description
Technical field
Invention relates to anode material for lithium-ion batteries, particularly to the system of a kind of lithium ion battery nickel cobalt aluminum positive electrode
Preparation Method.
Background technology
Lithium ion battery, due to the advantage such as its high-energy-density, security performance are preferable and cost is relatively low, is increasingly becoming the heaviest
The making active materials for use in secondary electrochemical cells wanted.The mobile devices such as current lithium ion battery successful Application mobile phone, panel computer the most, and,
It is successfully applied on hybrid-electric car and pure electric automobile.But, in pure electric automobile application, it is still desirable to further
The lithium ion battery energy density improved, thus promote pure electric automobile course continuation mileage.Owing to positive electrode is at lithium ion battery
Middle offer lithium source, the performance of battery is played a key effect by the performance of positive electrode, therefore, uses the positive pole material that energy density is high
Material is for promoting the energy density effective means of lithium ion battery.Up to the present, although nickel cobalt aluminum positive electrode
(LiNi0.8Co0.15Al0.05O2) it has been the positive electrode that energy density is the highest, and, it is applied to pure electric automobile
Lithium-ion-power cell, but, with LiNi0.8Co0.15Al0.05O2Energy density for positive electrode lithium ion battery is still hard to
Meet requirement (the new energy of the year two thousand twenty of " state key research and development plan new-energy automobile emphasis special project embodiment (exposure draft) "
Source automotive battery energy density reaches 300Wh/kg) requirement.In order to promote lithium-ion-power cell energy density further, have
Necessity promotes LiNi further0.8Co0.15Al0.05O2Energy density.It addition, the power density phase of existing lithium-ion-power cell
Contrasting relatively low, the charging interval causing pure electric automobile is longer.In order to shorten the charging interval of pure electric automobile, need to promote lithium
The power density of ion battery, it is therefore necessary to promote LiNi further0.8Co0.15Al0.05O2High rate performance.
Now there are some researches show: the property of positive electrode can be promoted further by controlling the pattern of lithium ion anode material
Energy.The second particle wherein regulating and controlling positive electrode is the square structural stability being conducive to improving material, and micro nano structure
Square granule can shorten lithium ion mobility path such that it is able to improve positive electrode chemical property (Journal of
Solid State Electrochemistry, 2013, 17:2589–2594; Journal of The
Electrochemical Society, 2016,163:A197 A202).Although design second particle is square pattern,
The chemical property of positive electrode can be promoted further, but, due to LiNi0.8Co0.15Al0.05O2The positive pole material of difficult synthesis
Material, using existing document report synthesis second particle is square LiMn2O4And LiMnO2Method Deng positive electrode, it is difficult to close
Becoming second particle is square LiNi0.8Co0.15Al0.05O2Positive electrode, it is difficult to realize promoting further
LiNi0.8Co0.15Al0.05O2Circulation volume (i.e. energy density) and the target of high rate performance.
Summary of the invention
It is an object of the invention to overcome prior art to be difficult to synthesize second particle is square LiNi0.8Co0.15Al0.05O2
The deficiency of positive electrode, it is provided that a kind of second particle is square nickel cobalt aluminum method for preparing anode material, thus promotes further
LiNi0.8Co0.15Al0.05O2Circulation volume and high rate performance；The method utilizes the effect of chelating agent first to prepare secondary
Grain is square presoma, then itself and aluminum contained compound and lithium-containing compound mixed calcining are prepared second particle is square
LiNi0.8Co0.15Al0.05O2Positive electrode, the LiNi that this preparation method obtains0.8Co0.15Al0.05O2Positive electrode second particle
Having square structure, electrochemical performance, and simple and reliable process, applicable second particle is square
LiNi0.8Co0.15Al0.05O2Positive electrode extensive, commercially produce.
In order to realize foregoing invention purpose, the invention provides the preparation of a kind of lithium ion battery nickel cobalt aluminum positive electrode
Method, its concrete preparation process is as follows:
(1) prepared by presoma: be stoichiometrically 0.8 0.15 to be dissolved in solvent by nickel compound containing and cobalt compound,
Adding chelating agent, carry out hydro-thermal reaction, obtaining second particle is square presoma；
(2) mixed calcining: presoma step 1 obtained mixes with aluminum contained compound and lithium-containing compound, calcine and obtain secondary
Granule is square LiNi0.8Co0.15Al0.05O2Positive electrode.
The preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode is the complexing utilizing chelating agent,
In hydrothermal reaction process, directly generate the presoma with square structure such that it is able to by square presoma and lithium-containing compound
Square LiNi is obtained with aluminum contained compound mixed calcining0.8Co0.15Al0.05O2Positive electrode.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, the nickeliferous chemical combination described in step 1
Thing is soluble nickel salt, it is preferred that described nickel compound containing is nickel acetate, nickel sulfate, one or more in nickel nitrate.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, described in step 1 containing cobalt chemical combination
Thing is soluble cobalt, it is preferred that described cobalt compound is cobalt acetate, cobaltous sulfate, one or more in cobalt nitrate.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, step 1 solvent dissolves nickeliferous chemical combination
In the solution formed after thing and cobalt compound, total concentration of metal ions is 0.1 ~ 2mol/L.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, the solvent described in step 1 is for going
Ionized water.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, the chelating agent described in step 1 is
NH4HCO3, one or both in carbamide；The usage amount of described chelating agent is chelating agent and Ni+Co in nickeliferous and cobalt compound
Mol ratio is 0.5-2.0 0.95.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, the hydro-thermal reaction described in step 1
Temperature be 150-200 DEG C；Response time is 6-20h；Preferably, the temperature of hydro-thermal reaction is 175 DEG C, and the response time is 12h.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, closing containing calorize described in step 2
Thing is one or more in aluminium hydroxide, aluminum nitrate, aluminum isopropylate.；The usage amount of described aluminum contained compound is rubbing of Al and Ni
Your ratio is 0.05 0.8.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, closing containing lithiumation described in step 2
Thing is one or more in Lithium hydrate, lithium nitrate, Quilonorm (SKB), lithium carbonate；The usage amount of described lithium-containing compound be Li with
The mol ratio of Ni is 1.05 0.8.
In the preparation method of above-mentioned a kind of lithium ion battery nickel cobalt aluminum positive electrode, the calcining described in step 2 uses
Calcine by steps technique, calcine by steps includes two sections, and wherein the temperature of first paragraph calcining is 300-500 DEG C, and the sintering soak time is
3-6h；Second segment calcining heat is 700-800 DEG C, and the sintering soak time is 10-25h；Preferably, the temperature of first paragraph calcining is
400 DEG C, the sintering soak time is 5h；Second segment calcining heat is 750 DEG C, and the sintering soak time is 18h.
Preferably, the preparation method of a kind of lithium ion battery nickel cobalt aluminum positive electrode, its concrete preparation process is as follows:
(1) prepared by presoma: be stoichiometrically 0.8 0.15 by water solublity nickel compound containing and water solublity cobalt compound
It is dissolved in deionized water, adds chelating agent, after stirring, pour solution into reactor, carry out hydro-thermal reaction；Then will be anti-
Answer product washing, be dried, it is thus achieved that second particle is square presoma.
(2) prepared by positive electrode: with deionized water as medium, by uniform with aluminum contained compound and lithium-containing compound for presoma
Mix, be dried；Then calcine by steps technique is used to calcine compound, it is thus achieved that second particle is square
LiNi0.8Co0.15Al0.05O2Positive electrode.
The inventive method is the complexing utilizing chelating agent, in hydrothermal reaction process, directly generates and has square knot
The presoma of structure such that it is able to square presoma is obtained square with lithium-containing compound and aluminum contained compound mixed calcining
LiNi0.8Co0.15Al0.05O2Positive electrode；And by optimizing preparation technology, make to prepare is square
LiNi0.8Co0.15Al0.05O2Positive electrode circulation volume and high rate performance are more excellent；The present invention prepares square
LiNi0.8Co0.15Al0.05O2The method simple and reliable process of positive electrode, applicable second particle is square
LiNi0.8Co0.15Al0.05O2Positive electrode extensive, commercially produce.
Compared with prior art, beneficial effects of the present invention:
1, the inventive method utilizes the complexing of chelating agent, it is possible to it is square for preparing second particle
LiNi0.8Co0.15Al0.05O2Positive electrode.
2, the second particle that the inventive method prepares is square LiNi0.8Co0.15Al0.05O2Positive electrode electrochemistry
Excellent performance.
3, the inventive method simple and reliable process, applicable second particle is square LiNi0.8Co0.15Al0.05O2Positive pole material
Material extensive, commercially produce.
Accompanying drawing illustrates:
Fig. 1 is that the present invention prepares LiNi0.8Co0.15Al0.05O2The process chart of positive electrode.
Fig. 2 is the nickel cobalt presoma synthesized with carbamide for chelating agent in embodiment 1 and prepared
LiNi0.8Co0.15Al0.05O2Positive electrode XRD figure spectrum (a is presoma, and b is positive electrode)
Fig. 3 is the nickel cobalt presoma and prepared LiNi synthesized with carbamide for chelating agent in embodiment 10.8Co0.15Al0.05O2Just
Pole material SEM collection of illustrative plates (a is presoma, and b is positive electrode)
Fig. 4 is the LiNi prepared with carbamide for the presoma that chelating agent synthesizes in embodiment 10.8Co0.15Al0.05O2Positive electrode and
Comparative example 2 uses LiNi prepared by business presoma0.8Co0.15Al0.05O2(a is first for the electrical property comparison diagram of positive electrode
Charging and discharging curve, b is high rate performance, and c is cycle performance).
Detailed description of the invention
Below in conjunction with comparative example and detailed description of the invention, the present invention is described in further detail.But this should not understood
Scope for the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to this
The scope of invention.
Embodiment 1
Weigh the C of 1.258g4H6O4Ni·4H2The C of O and 0.235g4H6O4Co·4H2O(mol ratio Ni Co=0.8 0.15), separately
Outward, the carbamide weighing 0.3g makees chelating agent, is dissolved in 80ml deionized water, is moved to by solution in 100mL reactor, will reaction
Still is placed in calorstat, and arranging reaction temperature is 175 DEG C, and the response time is 12 hours.After reaction terminates, it is washed with deionized
3 times.Being vacuum dried 12 hours by 50 DEG C of the product vacuum drying oven washed, (Fig. 2-a is institute to obtain precursor powder
The XRD figure spectrum of the presoma of preparation, Fig. 3-a is the SEM collection of illustrative plates of prepared presoma).According to Al (Ni+Co) mol ratio it is
The ratio of 0.05 0.95, and Li (Ni+Co+Al) mol ratio is the ratio of 1.05 1, by Lithium hydrate, aluminum isopropylate. and institute
Presoma processed uniformly mixes.By mixture in tube calciner, under oxygen atmosphere, it is incubated 5 hours with 400 DEG C, then temperature
It is increased to 750 DEG C, is incubated 18 hours, after furnace cooling, it is thus achieved that LiNi0.8Co0.15Al0.05O2(Fig. 2-b is prepared to positive electrode
Positive electrode XRD figure spectrum, Fig. 3-b is the SEM collection of illustrative plates of prepared positive electrode).With LiNi0.8Co0.15Al0.05O2For just
Pole material, is assembled into R2032 type button cell, at 25 DEG C, 2.8 ~ 4.3V, 18mA/g(0.1C) under the conditions of carry out charge and discharge electrical measurement
Examination, discharge capacity is 198mAh/g first, is 156mAh/g at 180mA/g discharge capacity, after 50 times circulate, electric discharge
Capacity is 145mAh/g, and capability retention is 92.9%.
Embodiment 2
Weigh the C of 1.258g4H6O4Ni·4H2The C of O and 0.235g4H6O4Co·4H2O(mol ratio Ni:Co=0.8 0.15), separately
Outward, the carbamide weighing 0.5g makees chelating agent, is dissolved in 80ml deionized water, is moved to by solution in 100mL reactor, will reaction
Still is placed in calorstat, and arranging reaction temperature is 200 DEG C, and the response time is 6 hours.After reaction terminates, it is washed with deionized 3
Secondary.50 DEG C of the product vacuum drying oven washed is vacuum dried 12 hours, obtains precursor powder.According to Al (Ni
+ Co) mol ratio is the ratio of 0.05 0.95, and Li (Ni+Co+Al) mol ratio is the ratio of 1.05 1, by lithium carbonate, hydrogen
Aluminium oxide uniformly mixes with made presoma.By mixture in tube calciner, under oxygen atmosphere, little with 500 DEG C of insulations 3
Time, then temperature is increased to 700 DEG C, is incubated 25 hours, after furnace cooling, it is thus achieved that LiNi0.8Co0.15Al0.05O2Positive electrode.With
LiNi0.8Co0.15Al0.05O2For positive electrode, it is assembled into R2032 type button cell, at 25 DEG C, 2.8 ~ 4.3V, 18mA/g
(0.1C) carrying out charge-discharge test under the conditions of, discharge capacity is 195mAh/g first, at 180mA/g discharge capacity is
158mAh/g, after 50 times circulate, discharge capacity is 146mAh/g, and capability retention is 92.4%.
Embodiment 3
Weigh the nickel sulfate of 1.317g and the cobaltous sulfate (mol ratio Ni Co=0.8 0.15) of 0.265g, it addition, weigh 0.25g's
NH4HCO3Make chelating agent, be dissolved in 80ml deionized water, move to solution, in 100mL reactor, reactor is placed in constant temperature
In case, arranging reaction temperature is 150 DEG C, and the response time is 20 hours.After reaction terminates, it is washed with deionized 3 times.Will washing
50 DEG C of vacuum drying oven of good product is vacuum dried 12 hours, obtains precursor powder.According to Al (Ni+Co) mole
Than be 0.05 0.95 ratio, and Li (Ni+Co+Al) mol ratio is the ratio of 1.05 1, by lithium nitrate, aluminium hydroxide with
Made presoma uniformly mixes.By mixture in tube calciner, under oxygen atmosphere, it is incubated 6 hours with 300 DEG C, then temperature
Degree is increased to 800 DEG C, is incubated 10 hours, after furnace cooling, it is thus achieved that LiNi0.8Co0.15Al0.05O2Positive electrode.With
LiNi0.8Co0.15Al0.05O2For positive electrode, it is assembled into R2032 type button cell, at 25 DEG C, 2.8 ~ 4.3V, 18mA/g
(0.1C) carrying out charge-discharge test under the conditions of, discharge capacity is 196mAh/g first, at 180mA/g discharge capacity is
159mAh/g, after 50 times circulate, discharge capacity is 145mAh/g, and capability retention is 91.2%.
Embodiment 4
Weigh the nickel nitrate of 1.470g and the cobalt nitrate (mol ratio Ni Co=0.8 0.15) of 0.275g, it addition, weigh 0.3g's
NH4HCO3Make chelating agent, be dissolved in 80ml deionized water, move to solution, in 100mL reactor, reactor is placed in constant temperature
In case, arranging reaction temperature is 200 DEG C, and the response time is 12 hours.After reaction terminates, it is washed with deionized 3 times.Will washing
50 DEG C of vacuum drying oven of good product is vacuum dried 12 hours, obtains precursor powder.According to Al (Ni+Co) mole
Ratio is the ratio of 0.05 0.95, and Li (Ni+Co+Al) mol ratio is the ratio of 1.05 1, by Quilonorm (SKB), aluminum nitrate and institute
Presoma processed uniformly mixes.By mixture in tube calciner, under oxygen atmosphere, it is incubated 5 hours with 500 DEG C, then temperature
It is increased to 750 DEG C, is incubated 18 hours, after furnace cooling, it is thus achieved that LiNi0.8Co0.15Al0.05O2Positive electrode.With
LiNi0.8Co0.15Al0.05O2For positive electrode, it is assembled into R2032 type button cell, at 25 DEG C, 2.8 ~ 4.3V, 18mA/g
(0.1C) carrying out charge-discharge test under the conditions of, discharge capacity is 195mAh/g first, at 180mA/g discharge capacity is
153mAh/g, after 50 times circulate, discharge capacity is 142mAh/g, and capability retention is 92.8%.
Comparative example 1
Weigh the C of 1.258g4H6O4Ni·4H2The C of O and 0.235g4H6O4Co·4H2O(mol ratio Ni Co=0.8 0.15), separately
Outward, the sodium hydroxide weighing 0.5g makees chelating agent, is dissolved in 80ml deionized water, is moved to by solution in 100mL reactor, will
Reactor is placed in calorstat, and arranging reaction temperature is 175 DEG C, and the response time is 12 hours.After reaction terminates, use deionized water
Wash 3 times.50 DEG C of the product vacuum drying oven washed is vacuum dried 12 hours, obtains the presoma of pattern rule
Powder.It is the ratio of 0.05 0.95 according to Al (Ni+Co) mol ratio, and Li (Ni+Co+Al) mol ratio is 1.05 1
Ratio, uniformly mixes Lithium hydrate, aluminum isopropylate. with made presoma.By mixture in tube calciner, oxygen atmosphere
Under, it is incubated 5 hours with 400 DEG C, then temperature is increased to 750 DEG C, is incubated 18 hours, after furnace cooling, it is thus achieved that
LiNi0.8Co0.15Al0.05O2Positive electrode.With LiNi0.8Co0.15Al0.05O2For positive electrode, it is assembled into R2032 type button electricity
Pond, at 25 DEG C, 2.8 ~ 4.3V, 18mA/g(0.1C) under the conditions of carry out charge-discharge test, discharge capacity is 193mAh/g first,
180mA/g discharge capacity is 149mAh/g, and after 50 times circulate, discharge capacity is 130mAh/g, and capability retention is
87.1%。
Comparative example 2
Use business spherical nickel-cobalt presoma, Lithium hydrate, aluminum isopropylate. are uniformly mixed with presoma.By mixture in tubular type
In calcining furnace, under oxygen atmosphere, being incubated 5 hours with 400 DEG C, then temperature is increased to 750 DEG C, is incubated 18 hours, furnace cooling
After, it is thus achieved that LiNi0.8Co0.15Al0.05O2Positive electrode.With LiNi0.8Co0.15Al0.05O2For positive electrode, it is assembled into R2032 type
Button cell, at 25 DEG C, 2.8 ~ 4.3 V, carry out charge-discharge test under the conditions of 18mA/g, discharge capacity is 192mAh/g first,
Being 150mAh/g at 180mA/g discharge capacity, after 50 times circulate, discharge capacity is 131mAh/g, capability retention
It is 87.3%.
Embodiment 1-4 and comparative example 1-2 are carried out electrochemical property test result such as following table:
| Embodiment | 0.1C discharge capacity (mAh/g) | 1C discharge capacity (mAh/g) | 10 C discharge capacities (mAh/g) | 1C circulates 50 discharge capacitances |
| Embodiment 1 | 198 | 156 | 87 | 92.9% |
| Embodiment 2 | 195 | 158 | 88 | 92.4% |
| Embodiment 3 | 196 | 159 | 73 | 91.2% |
| Embodiment 4 | 195 | 153 | 86 | 92.8% |
| Comparative example 1 | 193 | 149 | 61 | 87.2% |
| Comparative example 2 | 192 | 150 | 62 | 87.3% |
By to above-mentioned chemical property interpretation of result: the secondary that embodiment 1-4 uses the inventive method to prepare
Grain is square LiNi0.8Co0.15Al0.05O2Excellent for positive electrode, circulation volume and high rate performance, especially embodiment 1 is
Optimal case, obtains LiNi0.8Co0.15Al0.05O2For positive electrode, at 18mA/g(0.1C) under the conditions of carry out charge-discharge test,
Discharge capacity is 198mAh/g first, is 156mAh/g at 180mA/g discharge capacity, and after 50 times circulate, electric discharge is held
Amount is 145mAh/g, and capability retention is 92.9%；Comparative example 1 does not uses the inventive method, does not uses chelating agent of the present invention,
The LiNi arrived0.8Co0.15Al0.05O2Significantly reduce for positive electrode circulation volume and high rate performance, at 18mA/g(0.1C) condition
Under carry out charge-discharge test, discharge capacity is 193mAh/g first, is 149mAh/g at 180mA/g discharge capacity, through 50
After secondary circulation, discharge capacity is 130mAh/g, and capability retention is 87.1%, it is clear that comparative example 1 fails to prepare secondary
Granule is square LiNi0.8Co0.15Al0.05O2For positive electrode；Comparative example 2 uses existing spherical precursor to prepare gained
LiNi0.8Co0.15Al0.05O2For positive electrode, carrying out charge-discharge test under the conditions of 18mA/g, discharge capacity is first
192mAh/g, is 150mAh/g at 180mA/g discharge capacity, and after 50 times circulate, discharge capacity is 131mAh/g, holds
Amount conservation rate is 87.3%, and its circulation volume and the high rate performance second particle that substantially less than embodiment of the present invention 1 prepares is
Square LiNi0.8Co0.15Al0.05O2For positive electrode (Fig. 4).
Claims (10)
1. the lithium ion battery preparation method of nickel cobalt aluminum positive electrode, it is characterised in that include following preparation process:
(1) prepared by presoma: nickel compound containing and cobalt compound are dissolved in solvent, adds chelating agent, carries out hydro-thermal anti-
Should, obtaining second particle is square presoma；
(2) mixed calcining: presoma step 1 obtained mixes with aluminum contained compound and lithium-containing compound, calcine and obtain secondary
Granule is square LiNi0.8Co0.15Al0.05O2Positive electrode；
Described chelating agent is NH4HCO3, one or both in carbamide；Described nickel compound containing, cobalt compound, containing aluminum
In compound, lithium-containing compound, the mol ratio of Ni Co Al Li is 0.8 0.15 0.05 1.05.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
In 1, nickel compound containing is nickel acetate, nickel sulfate, one or more in nickel nitrate.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
In 1, cobalt compound is cobalt acetate, cobaltous sulfate, one or more in cobalt nitrate.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
The usage amount of 1 complexing agent is chelating agent and the mol ratio of Ni+Co in nickeliferous and cobalt compound is 0.5-2.0 0.95.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
In 1, the temperature of hydro-thermal reaction is 150-200 DEG C；Response time is 6-20h.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 5, it is characterised in that hydro-thermal
The temperature of reaction is 175 DEG C, and the response time is 12h.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
One or more during aluminum contained compound is aluminium hydroxide, aluminum nitrate, aluminum isopropylate. in 2.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
One or more during lithium-containing compound is Lithium hydrate, lithium nitrate, Quilonorm (SKB), lithium carbonate in 2.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 1, it is characterised in that step
In 2, calcining uses calcine by steps technique, and calcine by steps includes two sections, and wherein the temperature of first paragraph calcining is 300-500 DEG C, calcining
Temperature retention time is 3-6h；Second segment calcining heat is 700-800 DEG C, and the sintering soak time is 10-25h.
The preparation method of lithium ion battery nickel cobalt aluminum positive electrode the most according to claim 9, it is characterised in that the
The temperature of one section calcining is 400 DEG C, and the sintering soak time is 5h；Second segment calcining heat is 750 DEG C, and the sintering soak time is
18h。
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| CN110571411A (en) * | 2019-04-30 | 2019-12-13 | 湖北锂诺新能源科技有限公司 | ti doped and La4NiLiO8Preparation method of coated nickel-rich cathode material |
| CN110931772A (en) * | 2020-02-12 | 2020-03-27 | 湖南长远锂科股份有限公司 | Preparation method of high-power type positive electrode material for lithium ion battery |
| CN111009646A (en) * | 2019-12-09 | 2020-04-14 | 宁波容百新能源科技股份有限公司 | High-rate monocrystal-like nickel-cobalt lithium aluminate cathode material with coating layer and preparation method thereof |
| CN112831838A (en) * | 2020-12-31 | 2021-05-25 | 南通瑞翔新材料有限公司 | Preparation method of single crystal type nickel cobalt lithium aluminate anode material |
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