CN115196693A - LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery - Google Patents

LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery Download PDF

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CN115196693A
CN115196693A CN202210943776.1A CN202210943776A CN115196693A CN 115196693 A CN115196693 A CN 115196693A CN 202210943776 A CN202210943776 A CN 202210943776A CN 115196693 A CN115196693 A CN 115196693A
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libo
lialo
double
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positive electrode
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方明
丁何磊
罗学涛
许益伟
张旭
柴冠鹏
苏方哲
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Zhejiang Gepai Cobalt Industry New Material Co ltd
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Abstract

The invention discloses a LiBO 2 /LiAlO 2 Double-layer coated modified lithiumThe quaternary positive electrode material of the ion battery and the preparation method thereof are characterized in that the quaternary positive electrode material of nickel, cobalt, manganese and aluminum and LiBO coating the quaternary positive electrode material are used as the positive electrode material 2 /LiAlO 2 Forming; the chemical formula of the nickel-cobalt-manganese-aluminum quaternary positive electrode material is LiNi x Co y Mn z Al 1‑x‑y‑z O 2 . LiBO in the invention 2 /LiAlO 2 The double-layer coated modified quaternary positive electrode material of the lithium ion battery can effectively block side reactions of an electrode/electrolyte interface, thereby improving the cycling stability of the material.

Description

LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery
Technical Field
The invention belongs to the field of lithium ion secondary battery anode materials, and particularly relates to LiBO 2 /LiAlO 2 A method for preparing a quaternary NCMA positive electrode material of a double-layer coated modified lithium ion battery.
Background
With the progress of scientific technology and the rapid development of national economy, the living standard of people is increasingly improved, and the demand on energy is increased. However, fossil energy such as petroleum and coal is gradually exhausted, and meanwhile, environmental pollution is more and more serious, and human survival is threatened, so that alternative new energy sources are urgently needed to be searched. Renewable energy sources such as solar energy, wind energy and tidal energy enter the view of human beings, but large-scale application is limited by various factors such as regions. With the continuous exploration and development of new energy, various energy storage devices appear in succession, and lithium ion batteries are deeply valued. Compared with the traditional lead-acid battery, the lithium ion battery has unique advantages, such as high energy density, small self-discharge, long service life, environmental friendliness and the like, and is widely applied to various portable electronic devices. The anode material of the lithium ion battery at present mainly comprises lithium cobaltate, lithium iron phosphate, a ternary high nickel anode material and the like.
In the lithium ion battery, the anode material is easy to electrolyze with organic electrolyte due to the higher potentialThe liquid undergoes a side reaction, thereby deteriorating the performance of the battery. For ternary high nickel material, insufficient oxygen concentration and lithium content and high temperature can cause Ni in the synthesis process 2+ Move to the Li layer, resulting in Li + /Ni 2+ Mixed arrangement reduces the rate capability of the material; in the late stage of charging, ni occupies Li layer 2+ Will be oxidized to Ni with smaller ionic radius 3+ Causing the layered structure to collapse; the excess of transition metal occupying the Li layer also exacerbates the transformation of the lamellar phase into the spinel phase and even the halite phase, resulting in an increased capacity fade.
For nickel-rich layered materials, researchers have extensively studied two very typical lithium nickel cobalt aluminum oxides (NCA, liNi) x Co y Al 1−x−y O 2 ) And lithium nickel cobalt manganese oxide (NCM, liNi) x Co y Mn 1−x−y O 2 ). The research shows that the introduction of Al obviously improves the thermal stability and the cycling stability of the nickel-rich cathode. Therefore, al is introduced to form the NCMA quaternary precursor when synthesizing the precursor by the coprecipitation method. Due to the doping of Al, the volume shrinkage and expansion of the cathode material in the processes of lithium removal and lithium insertion are inhibited, and the stress concentration and the generation of microcracks are reduced. The NCMA system has both the thermal and cycling stability of the NCA system and the high capacity of the NCM system.
The structural stability and the electrochemical performance of the nickel-rich cathode material are improved by methods such as element doping, surface modification, concentration gradient structure and the like. The metal oxide coating prevents the surface of the electrode from directly contacting with organic electrolyte, so that the erosion and decomposition of the electrolyte to the electrode material are relieved. However, the metal oxide coating does not have any effect on reducing surface lithium residue. In addition, the improvement of performance of metal oxides is inherently limited due to their low ionic and electronic conductivity. Chinese patent CN 109119611B proposes a method for realizing the common modification of the ternary anode material by ion doping and surface coating by a one-step method. Chinese patent CN 113948707A discloses a cerium pyrophosphate coated and modified lithium ion battery ternary positive electrode material which can effectively block side reactions of an electrochemical interface. However, the above patents all coat metal oxides or pyrophosphate with low ionic conductivity, which has inherent limitation on the performance improvement of the positive electrode material.
Disclosure of Invention
It is an object of the present invention to provide LiBO with reduced surface side reactions 2 /LiAlO 2 The invention relates to a double-layer coated modified quaternary anode material of a lithium ion battery and a preparation method thereof, which realize the improvement of the stability of the quaternary anode material by regulating and controlling the addition amount of a coating agent in the secondary sintering process.
In order to achieve the purpose, the invention adopts the following technical scheme:
LiBO 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary positive electrode material of the lithium ion battery comprises the following steps:
the method comprises the following steps: uniformly mixing a quaternary material precursor with a lithium source, and then sintering in an oxygen atmosphere to obtain a quaternary anode material;
step two: adding a quaternary anode material and polyvinylpyrrolidone into absolute ethyl alcohol, and continuously stirring to form a uniform solution I;
step three: adding a coating agent into the solution I, and stirring for 30min to form a solution II; the coating agent is a boron source and an aluminum source; the LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is characterized by comprising the following steps of: the mass fraction of the quaternary anode material obtained by sintering in the first step is 0.01-5 wt%;
step four: centrifuging the solution II to obtain a solid, washing the collected solid with absolute ethyl alcohol, and drying in vacuum;
step five: sintering the obtained dry powder in an oxygen atmosphere to obtain LiBO 2 /LiAlO 2 Double-layer coated modified quaternary positive electrode material of the lithium ion battery;
the LiBO 2 /LiAlO 2 The chemical formula of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is LiNi x Co y Mn z Al 1-x-y-z O 2 ，0.8<x<1,0<y<0.1,0<z<0.1, and x + y + z<1。
In the first step, the lithium source is LiOH. H2O. The melting point of lithium hydroxide is about 470 ℃, and the melting point of another lithium source lithium carbonate is about 720 ℃; the synthesis temperature of the quaternary high-nickel anode material is about 720 ℃, so that only lithium hydroxide can be selected.
In the first step, the molar ratio of the lithium source to the quaternary material precursor is 0.95-1.05:1.
the sintering in the first step is gradient sintering, the first gradient temperature is 400-450 ℃, the pre-sintering time is 3-4h, the second gradient temperature is 700-780 ℃, and the sintering time is 10-14h. The first step is a pre-lithiation process with a lower temperature, which aims to enable lithium hydroxide to reach a melting point so as to be melted and be more fully contacted with a precursor, and then the temperature is raised to reach a reaction temperature.
The temperature rise rate of the gradient sintering is 2-10 ℃.
In the second step, the boron source is H 3 BO 3 (ii) a The aluminum source is Al 2 O 3 ，Al 2 (SO 4 ) 3 ,NaAlO 2 Or Al (NO) 3 ) 3 ·9H 2 One or more of O.
The temperature during stirring in the second and third steps was 0 ℃. Because aluminum ions need to be added in the coating step for full stirring, the aluminum ions are very easy to hydrolyze, and the hydrolysis reaction is an endothermic reaction, the stirring temperature is reduced, so that the hydrolysis of the aluminum ions can be effectively inhibited; since the centrifugation process is extremely short compared to the stirring process, the centrifugation (step four) may not need to be controlled at 0 ℃.
The temperature rise rate of the sintering in the step (5) is 2-10 ℃/min; the heating temperature for sintering is 400-550 ℃; sintering is carried out in an oxygen atmosphere; the sintering heat preservation time is 4-6 h.
According to the invention, the addition amount of the coating agent in the secondary sintering process is regulated and controlled, so that the cycle stability of the quaternary anode material is improved, the addition amount of the coating agent is limited to 0.01-5 wt%, and when the addition amount is too high, the content of active substances in the material is reduced, and the capacity is not favorably exerted; on the other hand, too much addition of the coating agent causes an excessively thick coating layer, which greatly inhibits charge transfer between the material bulk phase and the interface, and is not favorable for the rate capability of the material.
The invention has the following advantages:
formed LiBO 2 /LiAlO 2 The double-layer coating layer can effectively prevent the direct contact between the anode material and the electrolyte, reduce the corrosion of the electrolyte to the active material to the maximum extent and inhibit the occurrence of surface side reactions, thereby stabilizing the material interface and reducing the dissolution of transition metal ions; the cathode electrode was prepared by mixing an active material (80 wt% quaternary positive electrode material), acetylene black (10 wt%), and polyvinylidene fluoride (PVDF 10 wt%). The mixture was dissolved in NMP solvent, stirred to form a homogeneous slurry, then coated on an aluminum foil current collector and dried at 120 ℃ for 12 h. The mass of the electrode was loaded on a circular aluminum foil with a diameter of 12 mm. A CR2032 type button cell was assembled in an argon-filled glove box using a metallic lithium foil as a counter electrode, cellgard 2300 as a separator, and a mixture of 1M lipff 6 dissolved in Ethylene Carbonate (EC)/methyl carbonate (EMC) (1.
Drawings
FIG. 1 is an XRD spectrum of comparative example and example 1;
FIG. 2 is SEM pictures of comparative example and example 1;
FIG. 3 is TEM pictures of comparative example and example 1;
FIG. 4 is an EDS scan of example 1;
fig. 5 is a 1C cycle plot for comparative example and example 1.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the following.
Comparative example
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 And 4.476g of LiOH. H 2 And O is uniformly mixed (Li: TM = 1.05. And sieving the product with a 400-mesh sieve to obtain the NCMA90433 cathode material. The NCMA90433 positive pole materialThe material is insulated for 5h at 550 ℃ under the oxygen atmosphere, and the annealed NCMA90433 cathode material is obtained.
Example 1
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH H 2 And O is uniformly mixed (Li: TM = 1.05. The product is sieved by a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. Dissolving 10g of NCMA90433 cathode material and 1g of polyvinylpyrrolidone in 50ml of absolute ethanol, and stirring at 0 ℃ to obtain a solution I; take 0.045gH 3 BO 3 、0.005gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4 hr; placing the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5h to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
Example 2
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH H 2 And O is uniformly mixed (Li: TM = 1.05. The product is sieved by a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. Dissolving 10g of NCMA90433 cathode material and 1g of polyvinylpyrrolidone in 50ml of absolute ethanol, and stirring at 0 ℃ to obtain a solution I; take 0.09gH 3 BO 3 、0.01gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4h; placing the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5h to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
Example 3
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH H 2 And O is uniformly mixed (Li: TM = 1.05. And sieving the product with a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. 1g of polyvinylpyrrolidone and 1g of NCMA90433 as anode materials were dissolved in 50ml of absolute ethanol, and stirred at 0 ℃ to obtain a solution I; take 0.135gH 3 BO 3 、0.015gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4 hr; putting the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5 hours to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
Example 4
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH H 2 And O is uniformly mixed (Li: TM = 1.05. And sieving the product with a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. 1g of polyvinylpyrrolidone and 1g of NCMA90433 as anode materials were dissolved in 50ml of absolute ethanol, and stirred at 0 ℃ to obtain a solution I; take 0.18gH 3 BO 3 、0.02gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4h; placing the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5h to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
Example 5
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH. H 2 And O is uniformly mixed (Li: TM = 1.05. And sieving the product with a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. 1g of polyvinylpyrrolidone and 1g of NCMA90433 as anode materials were dissolved in 50ml of absolute ethanol, and stirred at 0 ℃ to obtain a solution I; take 0.225gH 3 BO 3 、0.075gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4 hr; placing the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5h to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
Example 6
10.000g of quaternary precursor material (Ni) 0.9 Co 0.04 Mn 0.03 Al 0.03 (OH) 2 ) And 4.476g of LiOH. H 2 And O is uniformly mixed (Li: TM = 1.05. And sieving the product with a 400-mesh sieve to obtain the nickel-cobalt-manganese-aluminum anode material. Dissolving 10g of NCMA90433 cathode material and 1g of polyvinylpyrrolidone in 50ml of absolute ethanol, and stirring at 0 ℃ to obtain a solution I; take 0.27gH 3 BO 3 、0.03gAl (NO 3 ) 3 ·9H 2 Adding O into the solution I, stirring at 0 deg.C for 30min to obtain solution II, centrifuging the solution II to obtain solid, washing with anhydrous ethanol, and vacuum drying at 120 deg.C for 4h; placing the dried powder in an oxygen atmosphere at 500 ℃ (the heating rate is 2-10 ℃) and preserving the heat for 5h to obtain LiBO 2 /LiAlO 2 The double-layer coating modified NCMA90433 cathode material.
The experimental results are as follows:
TABLE 1C CYCLE PERFORMANCE COMPARATIONS OF COMPARATIVE EXAMPLE AND EXAMPLE
Test conditions Capacity of 100 th circle Capacity retention rate
Comparative example 2.7-4.3V;1C 145.8 80.8%
Example 1 2.7-4.3V;1C 172.1 94.5%
Example 2 2.7-4.3V;1C 174.4 95.8%
Example 3 2.7-4.3V;1C 171.7 94.3%
Example 4 2.7-4.3V;1C 168.2 92.4%
Example 5 2.7-4.3V;1C 165.3 90.8
Example 6 2.7-4.3V;1C 161.5 88.7
The results show that the LiBO of the invention 2 /LiAlO 2 The strategy of double-layer coating modified quaternary positive electrode material of the lithium ion battery greatly improves the cycle stability of the positive electrode material. And the cycle retention rate is increased and decreased with the gradual increase of the coating amount, which indicates that excessive coating is not suitable.
The above-mentioned embodiments are only used for explaining the inventive concept of the present invention, and do not limit the protection of the claims of the present invention, and any insubstantial modifications of the present invention using this concept shall fall within the protection scope of the present invention.

Claims (8)

1. LiBO 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary anode material of the lithium ion battery is characterized by comprising the following steps of:
the method comprises the following steps: uniformly mixing a quaternary material precursor with a lithium source, and then sintering in an oxygen atmosphere to obtain a quaternary positive electrode material;
step two: adding a quaternary anode material and polyvinylpyrrolidone into absolute ethyl alcohol, and continuously stirring to form a uniform solution I;
step three: adding a coating agent into the solution I, and stirring for 30min to form a solution II; the coating agent is a boron source and an aluminum source; the mass fraction of the quaternary positive electrode material obtained by sintering in the first step is 100wt%, and the mass fraction of the coating agent is 0.01-5 wt%;
step four: centrifuging the solution II to obtain a solid, washing the collected solid with absolute ethyl alcohol, and drying in vacuum;
step five: sintering the obtained dry powder in an oxygen atmosphere to obtain LiBO 2 /LiAlO 2 Double-layer coated modified quaternary positive electrode material of the lithium ion battery;
the LiBO 2 /LiAlO 2 The chemical formula of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is LiNi x Co y Mn z Al 1-x-y-z O 2 ，0.8<x<1,0<y<0.1,0<z<0.1, and x + y + z<1。
2. The LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary anode material of the lithium ion battery is characterized by comprising the following steps of: in the step one, the lithium source is LiOH. H 2 O。
3. The LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is characterized by comprising the following steps of: in the first step, the molar ratio of the lithium source to the quaternary material precursor is 0.95-1.05:1.
4. the LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is characterized by comprising the following steps of: the sintering in the first step is gradient sintering, the first gradient temperature is 400-450 ℃, the pre-sintering time is 3-4h, the second gradient temperature is 700-780 ℃, and the sintering time is 10-14h.
5. The LiBO of claim 4 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary anode material of the lithium ion battery is characterized by comprising the following steps of: the temperature rise rate of the gradient sintering is 2-10 ℃.
6. The LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary positive electrode material of the lithium ion battery is characterized by comprising the following steps of: in the second step, a boron sourceIs H 3 BO 3 (ii) a The aluminum source is Al 2 O 3 ，Al 2 (SO 4 ) 3 ,NaAlO 2 Or Al (NO) 3 ) 3 ·9H 2 One or more of O.
7. The LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary anode material of the lithium ion battery is characterized by comprising the following steps of: the temperature during stirring in the second and third steps was 0 ℃.
8. The LiBO of claim 1 2 /LiAlO 2 The preparation method of the double-layer coated modified quaternary anode material of the lithium ion battery is characterized by comprising the following steps of: the temperature rise rate of the sintering in the step (5) is 2-10 ℃/min; the heating temperature for sintering is 400-550 ℃; sintering is carried out in an oxygen atmosphere; the sintering heat preservation time is 4-6 h.
CN202210943776.1A 2022-08-08 2022-08-08 LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery Pending CN115196693A (en)

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Application publication date: 20221018